J A. Pizzi: New Approach to Non-Toxic Wood Preservatives.

Part I 253

i Holzforschung
47 (1993) 253-260

ANew Approach to Non-Toxic, Wide-Spectrum, Ground-Contact

Wood Preservatives
Part I. Approach and Reaction Mechanisms
By A. Pizzi
Department of Chemistry, University of the Witwatersrand, Johannesburg, South Africa

words Summary
CNon^tox^wood preservatives^ Copper soaps with carboxylic acid groups of unsaturated fatty acids of edible vegetable oils which are
QLJnsaturatecQfatty acids ** non-toxic, such as corn (maize) oil, of resin acids of rosin which are non-toxic, and even of synthetic
Rosin (Cu soaps) unsaturated polyester resins were shown to have effectiveness and long-term durability as ground contact
Polyesters wood preservatives. 25 years-long tests against termites and fugal attack showed their long term effective-
Fixation ness. Their mechanism of action was shown, by model compounds reactions, to be based on their fixation
by three radical-induced reactions to the wood constituents matrix by (i) self-polymerisation, (ii) co-reac-
tion with carbon-carbon double bonds of lignin and (iii) co-reaction with lignin aromatic nuclei. Mecha-
nisms and reactions rate constants were obtained and are presented. Fixation is obtained at ambient tem-
perature, but can be accelerated to useful reaction times by moderate heat application or by the use at
ambient temperature of radical initiator couples (redox or other), as well as by ultraviolet radiation. Cu2+
was the biocide species used, although the system is shown to work with other biocides as well (PCP).
Cu2"1" is attached to the preservative network through the — COOH groups supplied by the organic part
of the preservative. Its binding constant in such an ionic bond is then much stronger than for coordination
type bonds, hence its long durability.The biocidal mechanism is based on the release of Cu2+ by hydrolysis
of the — (COO)~)2Cu2"1" bonds under humid to very humid conditions and on the reforming of the same
bond on redrying of the treated timber in service.This wood preservation system can then be summarized
as a mode of increasing long-term biocides performances in the treated timber by allowing the biocide
to be free when needed while remaining fixed when not needed. Other contributory factors are present.
A similar system involving esterification of PCP with the —COOH groups of resin yielded an equivalent
effect.

Introduction sote and CCA while still presenting excellent perfor-

The field of exterior, wide-spectrum, ground-contact mance, is very much topical. The problem is by no
wood preservatives is dominated to-day by the creoso- means simple. Low toxicity preservatives have been
tes and by chrome-based water-borne preservatives, prepared before but, their performance was vastly in-
particularly CCA. The use of other preservatives, ferior to that of creosote and CCA, or their cost was so
such as, in particular, organic-solvent PCP, has con- high (Pizzi et al. 1986) to practically render unfeasible
siderably decreased and is still decreasing further, the use of such materials in industrial applications.This
There is no doubt that creosote, CCA and PCP are ef- paper deals with a new principle leading to non-toxic
fective ground-contact wood preservatives, but the in- and low toxicity wood preservatives of excellent perfor-
creased environmental awareness in the last decades mance, and of comparable cost to the existing ground
of this century has also highlighted their problematic contact, wide-spectrum preservatives.
use from a toxicological point of view. In short, all
these preservatives are toxic. To be sure the effect of Approach
their toxicity has been minimized as best as possible The principle involved is to build in the wood a solid,
by the industries using them, but these practices do insoluble polymer network which might or might not"
not eliminate their main intrinsic problem, their toxi- need to be covalently bonded to the wood matrix,
city. Thus, CCA and creosote have already been provi- onto which is fixed by reasonably moisture labile
sionally banned by the U.S.A. Environmental Protec- bonds, a substance with fungicidal and termiticidal ac-
tion Agency (Keitt and Cummings 1977; USDA1980). tivity. Thus, wheii moisture is not present in the timber
Such ban however, had to be revoked simply because the active substance will remain attached to the synth-
no lower toxicity, or non-toxic, alternatives existed etic polymeric network. When moisture enters the
which could take these preservatives place. In this timber the bonds holding the biocide hydrolise and
scenario the search for low-toxicity or non-toxic the freed biocide counteracts the biological attack in
timber preservatives, which could substitute for creo- progress. As the timber redries the bonds be-
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254
tween the biocide and the polymer network are re-
formed. In brief, the system is based on the increase
of permanence of the biocide in the timber by this
mechanism. Many systems to achieve this aim can be
thought of and devised.This paper will concentrate on
a few of the most effective ones and indicate which
others work less well by this mechanism.
The first choice to be made is which biocide to use. A
safe one from a low mammalian toxicity point of view
is Copper (Fühner 1955). An example of this system
working with a toxic biocide, PCP, will also be pre-
sented for completions's sake.
The second choice to be made is which molecules can
be used to form the polymer network, linked or not
linked to the wood, although the former is preferable,
and which also carry groups that can both easily bind
the biocide as well as fairly easily hydrolise in humid
or wet conditions. The binding constants of the coordi-
nation bonds of copper with lignin guajacyl and syrin-
gyl groups indicate that these bonds may be too labile
to be able to undertake successfully the mechanism
sought. The binding constants of Copper with organic
carboxylic acid functions, —COOH, to form ionic
copper salts are however higher (Gillespie et al. 1986)
and this was the group which was chosen to fix Cop-
per(II) as biocide. Ionic bonds after all have energies
of 600—1100 kJ mole"1, while coordination bonds
have energies of only 110—350 kJ mole"1 (Kinloch
1987).
The mechanism of cross-linking to form a polymer
network can be very varied. The resin system chosen
in this work, as it proved to be the most effective, and
this does not exclude that better mechanisms or better
resins might be found, was however based on the rad-
ical cross-linking occurring by opening of carbon-car-
bon double bonds. Such mechanism is well known for
instance in the field of unsaturated polyesters (Paauw
and Pizzi 1991a, b).
-c=c
etc.
chain reaction to
solid polymer network
Thus, any compound containing carbon-carbon dou-
ble bonds, especially linear polymers, but not only
polymers or linear polymers, can cross-link, theoreti-
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A. Pizzi: New Approach to Non-Toxic Wood Preservatives. Part I
cally to a solid network by this mechanism. Thus, the
material which can be chosen to form such a solid net-
work may be of reasonably high molecular weight
(not necessarily polymeric), they must contain car-
bon-carbon double bonds unsaturations, and must
present one or more carboxylic acid-COOH function
to fix Cu2+ with the desired balance of strength. Many
well known materials come readily to mind with the
above characteristics. In this work three were chosen,
namely linear unsaturated polyesters, and two natural
materials, raw oils high in unsaturated fatty acids and
rosin. Linear unsaturated polyesters of the simpler
kind are the products of reaction of phthalic and
maleic anhydride with a polyol, generally propylene
glycol (Fig. 1).
H2C—OH
Maleic Phtalic Propylene
Anhydride Anhydride Glycol
CH 7 CH,
-CH-CH^-O—C—CH— CH-C—O^-CH—CH^—O—C^ JO**· 2H20
Fig. 1. condensation of maleic and phthalic anhydrides with pro-
pylene glycol to form linear unsaturated polyesters. Note that the
reactive unsaturation originates from the maleic anhydride residue.
The aromatic ring of the phthalic anhydride residue in the linear
chain can also participate in cross-linking but at a much slower rate
(Paauw and Pizzi 1991a, b).
The residual unsaturation in the system is supplied by the maleic
anhydride residues in the linear polymer chain. The interest in this
type of materials is that, contrary to the other natural materials de-
scribed and tested, the percentage of unsaturation for length of
polymer can be varied according to the relative proportions of
maleic and phthalic anhydride. Any proportions 10:90 to 90:10 of
maleic:phthalic can be used, and even 100% maleic polyesters
(Paauw and Pizzi 1991a) or 100% phthalic ones are not unknown
(Paauw and Pizzi 1991b).They also have the further advantage that
the polymeric chain length can be tailor-made according to needs,
hence giving to the resins a great flexibility in physical properties
such as viscosity, which may be important for penetration, and the
quantity of Cu2+ which can be fixed onto the chain. The carboxylic
acid functions are the ones situated at the end of the polymer and
obtained by the opening of the anhydride rings.
The second class of compounds is also of considerable
interest. To use pure unsaturated fatty acids oils, of
course, would be far too costly. However, linseed oil,
corn oil, sunflower oil, tung oil and other vegetable
drying and non-drying oils are particularly rich in
these compounds. Thus, natural or better, enriched
oils mixtures of oleic, linoleic and linolenic acid,
of linear CIS chain length and containing -COOH
groups would appear particularly suitable. Their great
 A. Pizzi: New Approach to Non-Toxic Wood Preservatives. Part I
attraction is that if corn oil or sunflower oil are used
these are completely non-toxic natural materials and
so is the Cu soap derived from them.Their cost is also
fairly low and they are produced in great quantities
worldwide for alimentary purposes. The main prob-
lem here is that the level of unsaturation is fixed, one
unsaturation for oleic, two unsaturations for linoleic
etc. Although the percentage of unsaturation can be
varied within certain limits by changing the percent-
ages of different fatty acids in the mixture by mixing
various oils, this variation is in effect limited to a very
small range. Although this may not seem to matter it
will be shown later that it many constitute a draw-
back.
The third material, also of natural origin and non-
toxic, which can be suggested rosin. Rosin is an
oleoresin which contains a very high proportion (be-
tween 60%—80%) of resin acids and abietic acid,
pimaric and levopimaric acid, palmitic acid and others
(Fengel andWegener 1984). A closer look at the struc-
ture of these compounds shows that unsaturated car-
bon-carbon double bonds of a non-aromatic nature
are always present. Carboxylic acid (-COOH) func-
tions are also always present.
:OOH :OOH
Pimaric Acid Abietic Acid Levopimaric Acid
This material was used to check the mechanism proposed not only
by forming Cu2+ salts with the carboxylic acid groups according to
the mechanism already proposed, but also to form esters with the
phenolic hydroxy groups of pentachlorophenol to obtain the same
mechanism with an hydrolyzable ester bond, decrease volatility and
increase durability of a toxic preservative such as PCP. The advan-
tages of rosin are that such material is non-toxic, it is a natural mate^
rial, has a relatively low cost, and can be obtained as a waste in great
quantities. The advantage of rosin, of course, is that it is a solid at
ambient temperature and easily forms a network even without
polymerizing, thus the need for polymerization and coreaction with
the wood constituents network is much lower than the other mate-
rials. Thus, resinites from pulp mills in which resin is already par-
tially resinified can easily be used for the purpose as part of the reac^
tion, that of self-polymerization has already been carried out.
Experimental
Preparation of preservative salts
1. Cu salt of rosin (resin acids): rosin (0.05 rnols, 15.123 g) was dis-
solved in ethanol (15 ml) at 50°C. After cooling the solution to
room temperature 50 ml of 1 molar sodium hydroxide solution
was added in 5 ml amounts. To the orange coloured solution of
Na salts of resin acids 50 ml of 1 molar copper sulphate was
added always under mechanical stirring. A suspension of blue
particles in a viscous green liquor was obtained. After centrifu-
gation three layers were obtained. The top layer was a viscous,
green liquor, the middle layer consisted of a blue liquid and the
bottom layer consisted of a solid blue copper soap of rosin. On
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255
addition of water to the viscous green layer, precipitation of a
further amount of blue copper soap of rosin was obtained. The
solid copper soap of rosin was filtered and the soap dried at 50 °C
for 245 hours.
2. Cu salt of corn oil (Zhea mays):The same procedure as for rosin
(above) was followed to produce a blue Cu soap of the unsatu-
rated fatty acids in corn oil.
3. Cu salt of unsaturated polyester resin: a polyester resin 50:50
maleic anhydride: phthalic anhydride, using propylene glycol as
a polyol was prepared as already reported (Paauw and Pizzi
1991a). After cooling the polyester resin, 1 molar sodium hydro-
xide solution was added to the polyester causing a very exother-
mic reaction. The reaction resulted in a viscous, cream mixture.
After cooling 1 molar copper suphate solution was added to the
mixture. A copper soap layer formed on top and was skimmed
away. Upon removal of the first layer, it reformed. All the sub-
sequent layers of the copper salt of the polyester resin were col-
lected.
Reaction kinetics
Reactions of Cu salts of unsaturated polyester, rosin and corn oil
To the polyester-Cu salt formed dissolved in xylene were added 2%
methylethyl ketone peroxide (MEKP) and 2% Cobalt naphthenate
accelerator. The kinetics of the self-condensation reaction were fol-
lowed by FT-IR by relating the variations of the intensities of the
IR bands at 1430 cm"1 and 780 cm"1; the former indicating the vari-
ation of the carbon-carbon double bond belonging to the styrene
present in the polyester resin and the latter indicating the variation
of the polyester resin skeletal carbon-carbon double bond. The
reaction was carried out at the different temperatures shown in
Table 1, where the 2nd order rate constant obtained are also re-
ported (k] rate constants). To the polyester-Cu salt 9.1 g, diluted in
5 ml xylene, 3.1 g guaiacol was added and 2% MEKP and 2% Co
naphtenate added. The reaction kinetics were followed by FT-IR by
the variation of the 900 cm"1 and 780 cm"1 bands, the former due
among others to the increase of the proportion of 1, 2, 4-trisubsti-
tuted aromatic rings due to guaiacol reactions (Pizzi 1990; Paauw
and Pizzi 1991b).The apparent rate constants obtained are shown
in Table 1 under the range of conditions used. (k3 rate constants).
To the polyester-Cu salt dissolved in xylene as above an equivalent
amount of styrene was added and 2% MEKP and 2% Co naphthe-
nate. The reaction kinetics were followed as above by FT-IR. The
results obtained are reported in Table 1 (k2 rate constants).
The same reactions were carried out at 25 °C and with variable per-
centages of MEKP (initiator) and Co naphthenate (accelerator).
The k t , k2 and k3 apparent rate constants are shown in Table 2.
The same reactions as above, but in a more limited range of temper-
atures, accelerated by UV light as a radical initiator or by the same
percentage of MEKP initiator and Co naphthenate accelerator,
were also carried out and followed by the same system of FT-IR
analysis. The results obtained and the apparent rate constants ob-
tained are shown in Tables 3 and 4.
Results and Discussion
The results in Table 1, 2, 3 and 4 are an indication of
the rate of reaction of the three different materials
under examination. Fundamentally three reactions
mainly occur or can occur: (i) the self-polymerization
of the organic material to form a solid network, (ii)
the reaction of the organic material with the carbon-
carbon double bonds of the lignin in the solid matrix
and, more randomly also (iii) the reaction of the or-
ganic material with some of the aromatic nuclei of
Holzforschung /Vol. 47 /1993 / No. 3
256 A. Pizzi: New Approach to Non-Toxic Wood Preservatives. Part I

wood lignin. The discussion, from the reaction kine- Table 1. Comparative values of the calculated (Arrhenius equa-
tics point of view, will be carried out here mainly in tion (6) see text) rate constants k t , k2 and k3 at different tempera-
tures of the reaction of Cu2+ soap of a 10/90 maleic/phthalic polyes-
function of the resins in which these reactions can be ter resin wood preservative. Initiator + accelerator 2% Cobalt
more easily observed, namely the unsaturated poyl- naphthenate + 2% MEK peroxide.
ester/Cu soap. The same approach has been used and
is valid also for the two unsaturated natural materials. Tempe- ki k2 k3
rature (/xmor'xs" 1 ) (/xmor'xs 1 · 1 ) (/xmol^xs" 1 )
The self-polymerization reaction
The first reaction, the self-polymerization of the 25 2.04 x ΙΟ"4 8.2 x ΙΟ"5 2.34 Χ ΙΟ"5
polyester resin, can be followed from the relative vari- 35 4.71 x ΙΟ"4 9.63 x ΙΟ"5 3.24 Χ ΙΟ"5
50 1.51 x ΙΟ"3 1.20 x ΙΟ"4 5.11 x ΙΟ"5
ation in intensity of the FT-IR bands at 1490 and 780 60 3.08 x ΙΟ"3 1.38 x ΙΟ"4 6.75 x ΙΟ"5
cm~].The former indicate the variation of the carbon- 70 6.05 x ΙΟ"3 1.57 x ΙΟ"4 8,79 x ΙΟ"5
carbon double bond of the styrene monomer in the 80 1.14 χ ΙΟ"3 1.77 x ΙΟ"4 1,13 x ΙΟ"4
normal proportions present in the resin while the lat-
ter is an indication of the variation of the polyester
resin skeletal carbon-carbon double bond. The reac-
tion was carried out at 25°C, 35°C and at 60°C. As the
reaction of the resin itself was the one of interest, the Reaction of preservative with C—C double bonds of
ratio of the two bands areas as a function of the reac- lignin model compounds
tion time was followed. Logarithmic curves of coeffi- Styrene was used as a simple model compound of the
cients of correlations r = 0,989 (at 25°C), r = 0,982 carbon-carbon double bonds of lignin. The polyester
(at 25°C) ancTr = 0,981 (at 60°C) were obtained. resin is used here also as a model compound of the
These allowed the calculation of the second order rate unsaturated natural materials.
constant of self-polymerization of a 10/90 maleic/ The FT-IR bands at 1490 cm"1 is due to free styrene
phthalic polyester resin according to the equation (1): which is always present in the resin. The relative inten-
sity of this band increases considerably when an ex-
= k,t (1) cess of styrene is added to model the carbon-carbon
[polyester]0 [polyester]t
double bond of the phenylpropane unit of lignin in
where wood. The 780 cm'1 band is due to the unconjugated
carbon-carbon double bonds in the polyester resin
[polyester]0 =
polyester molar concentration at time = 0 skeleton derived from the maleic residue; equally so
[polyester]t = is the 740 cm"1 band, but because a styrene band is
polyester molar concentration at time = t superimposed on5 it was decided to use the ratio of the
k! = rate constant of the reaction 740 band, which varies little or not at all and of the
t = time of reaction in seconds 780 cm"1 band to determine the disappearance of the
carbon-carbon double bonds, due to the resin. In the
The values of the rate constants obtained for this reac- case of the styrene's carbon-carbon double bond dis-
tion are shown in Table 1. From these, the law of de- appearance, the same procedure was adopted and the
pendance of the rate constant from the temperature ratio of the relevant 1490 cm"1 band and of the invar-
was calculated to be, in the form of the Arrhenius equ- iable 1620 cm"1 band was used. Both ratios followed
ation (2): logarithmic curves as a function of reaction time with
15307 coefficients of correlation r = 0,946 and r = 0,703 in
= 7,534 - (2) the case of the former and of the latter ratios respec-
2,303 RT
tively. The second order rate constant k2 was calcu-
where k is the rate constant, R is the Boltzmann con- lated on the basis of the integrated equation (3).
stant = 1,987 cal/g · mole andTis the temperature in
degrees Kelvin; 15307 is the energy of activation in 2,303
cal x mole"1 of the self-polymerization reaction. In [polyester]0 - [styrene]o 10 (3)
Table 1 are shown the calculated values of the rate [polyester]t [styrene]Q _
constants obtained from equation (2) at different tem- = - k2t
[styrene]t [polyester]o
peratures. The rate constant Iq values in Table 1 show
that the self-polymerization of the resin proceeds with The reaction was followed at 25°C, 50°C and70°C and
increasing rapidity as the temperature of reaction0 in- the rate constants obtained are also shown in Table 1.
creases. Thus for example, from Table 1 and at parity An equation to determine the dependence of this reac-
of reagents concentration, the self-polymerization tion from the temperature was determined in the form
proceeds 7,5 times faster at 50 °C than at 25 °C. of the following Arrhenius equation (4):
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 A. Pizzi: New Approach to Non-Toxic Wood Preservatives. Part I 257

2911 2,303 (polyester] t [guaiacol) 0

log in -1,9509- (4)
2,303 RT [polyester]0 - [guaiacol]0 [guaiacol] t [polyester] 0
where the energy of activation is of 2911 cal/molc. In OCH OCH,

this case the rate constant k2, hence the speed of the
- CH
reaction also increases with increasing temperature
but at a much slower rate than for the self-polymeriza- (5)
tion of the resin alone. unsaturated Cu soap 1,2,4 trisubstituted benzene ring
Rl C-CR 2
Reaction of preservative with lignin guaiacyl CH 2 -CH CH2—
units model compounds
This reaction is more rare and much more difficult to
Unsaturoted Cu Styrene Product
delect, to follow and to measure. The FT-IR band at soap
900 cm 1 is due among others to 1,2,4-trisubstituted
aromatic rings while the 780 cm1 one is the already de-
scribed one of the carbon-carbon double polyester The experimental rate constants obtained at 50°, 60°
skeleton. The increase in intensity of the 900 cm""1 and 70 °C for the various soaps are shown in Tables I,
band is a strong indication that a reaction between the 2,3 and 4. It was not possible to follow experimentally
skeletal polyester carbon-carbon double bonds and this reaction at lower temperatures as the reaction ap-
the aromatic ring of the guaiacol occurs. From the re- pears to be slow, erratic and very difficult to follow
lative variations of these two bands it was possible to and confusing results are obtained.The determination
calculate the rate constant k3 of this reaction accord- of the Arrhenius equation of dependance of k3 from
ing to the integrated expression. the reaction temperature (6):

Table 2. Dcpcnclancc of rate constants from percentages of initiator (MEKP) and accelerator (Co naphthenate) at 25°C of the reaction
of the Cu 2 ' soap of a 10/90 maleic/phthalic polyester resin used as a wood preservative

ji k, k2 Fixation react ion

£ Co naphthenate MEKP (/ x mol"1 x s"1) (/ x mol""1 x s"1) half-times (min)

: 0.5% 0.5% 3,63 x ΚΓ5 1.91 x ΚΓ5 301

1 1.0% 0.5% 5.02 x 10 ~5 2.64 x 10~5 217
2.0% 0.5% 1.10 x ΗΓ4 5.79 Χ Κ)'5 99
0.5% .0% 6.05 x 10~5 3.18 x 10~5 180
1 .0% .0% 7.40 x ΙΟ'5 3.89 x 10~5 147
2.0% .0% 1.27 x 10"4 6.32 x 10"5 86
0.5% .5% 8.17 x 10~5 4.30 X 10~5 134
! ι .0% .5% 9.29 x 10'5 4.89 X 10"5 117
2.0% .5% 1.37 X 10~4 7.21 X 10~5 80
0.5% 2.0% 1.01 X 10~4 5.31 x 10"5 108
': 1.0% 2.0% 1.09 Χ ΗΓ4 5.74 x 10"5 100
: 2.0% 2.0% 1.45 X 10~4 7.63 x 10~5 75

Table 3. Comparative values of the experimental rate constants kj, k2 and k3 for sunflower oil unsaluratcd fatty acids self-polymerization
and fixation reactions

Temperature Initiator k, k2 k3
(°C) type (/ x mol~' x s"1)
25 10"5 10~5 0.5 x 10"5
i Heat alone 1.08 x 0.9 x
50 Heat alone 1.34 x K)"4 1.67 x 10"5 1.60 X 10·5
70 Heat alone 1.35 X ΗΓ4 5.30 x 10 "5
—
80 Heat alone 2.26 X K)"4 4.80 x 10'5 4.20 X 10~5
100 Heat alone 2.45 x 10'4 3.00 x ΗΓ5 -
25 UV 1.48 x ΙΟ'5 1.49 x 1Q~5 ~
60 Peroxide 3.00 Χ ΙΟ'3* 2.77 x 10"4 0.96 X 10~5
(2% MEKP
1 2% cobalt
naphthenate

— not measured because too difficult to quantify, or not detected

* uncertain value

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258
Table 4. Comparative values of the experimental rate constants
k,, k2 and k3 for rosin used as surface finish
Tempc- Initiator k,
rature type (in/ x mol"1 x s"1)
60 Peroxide -* 1.41 x 10~4 9.1 x 10~5
* This reaction does not appear to occur, probably because rosin
already in resinite form.
5982
Iog 10 k 3 = -0,2448 - (6)
2,303 RT
for this reaction allowed rather to calculate the values
of the k3 rate constant at lower temperatures for the
polyester resin. The values obtained indicate that this
reaction is indeed too slow at ambient temperature to
compete with the previous two reactions.The reaction
does occur, but at ambient temperature in less than
1/9 of the rate of the self-polymerization reaction and
less than 1/3 of the rate of the second reaction.
Comparison of the three fixation reactions rate
InTable 1 all the calculated rate constants at different temperatures
for the three reactions contributing to fixation are presented. At am-
bient temperature the experimental self-polymerization reaction
(k! = 1.45) 10~4) is approximately twice (1,9 times) faster than the
chemical fixation of the resin to the carbon-carbon double bond of
the phenylpropane unit of lignin. Both these reactions are much fas-
ter than the reaction between the resin and the aromatic ring of the
guaiacol. Thus, in the normal ambient temperature application of
these resins to wood as a preservative the third reaction can be
sometimes disregarded. Of further importance is the fact that as the
temperature increases the rate of self-polymerization becomes even
faster than the rate of reaction between resin and lignin.Thus, from
Table 1 at 50°C it has become 12 times faster and at 70°C almost 39
times faster. Even at 35 °C, by only increasing the temperature of
only ten degrees the resin self-polymerization becomes already 5 to
7 times faster than the chemical fixation of the resin to lignin (cf.
Tables 1, 2, 3 and 4).
Durability of this type of preservative in relation to the two main
reactions outlined, is determined by the irreversible fixation to the
wood matrix (the second reaction) and also by the self-polymeriza-
tion of the resin. The former reaction ensures that the hardened
resin matrix is irreversibly chemically anchored to the wood matrix
and ensures that at least part of it cannot be detached from the
wood it permeates. It is clear hence, that the optimal durability of
these preservatives may depend from an adequate balance of the
two reactions taking place. The inference is that by applying the
resin at higher temperatures may well affect weatherability of the
preservative with perhaps toughening the surface against purely
mechanical and dimensional wear. The conclusion must then be that
such preservatives should perform best when applied and cured in
the approximate temperature range of 20 to 30°C. Outside this
range a shift in the type of durability might be obtained from that
already observed in field tests. At lower temperatures, while a
higher level of solvent may also need to be added to maintain penet-
rability, weather durability in the form of UV resistance and water
capability to displace the resin from the wood, will be conserved or
even be improved. However, the rate of curing and hardening of
the resin will be sharply lengthened and fixation might become ex-
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A. Pizzi: New Approach to Non-Toxic Wood Preservatives. Part I
cessively long; this, also at the expense of decreased mechanical
wear resistance. At higher temperatures the proportion of real
chemical fixation of the finish to the wood matrix may become prog-
ressively less, weather durability may be expected to decrease and
resistance to mechanical wear and dimensional variation to im-
prove. This, of course, if the Cobalt naphthenate, MEK peroxide
system of acceleration is used. If one compares temperature alone,
as the cross-linking system, without the peroxide, the efficiency of
linking is very much worse than by using the peroxide system at
higher temperatures. Temperature alone, as a system of fixation
should not be recommended as the field results may be very differ-
ent from those obtained at ambient temperature.
Dependance of reaction rates from the percentages of initiator
and catalyst
All the results presented up to now have been obtained by the addi-
tion of 2.0% Cobalt naphthenate as a catalyst and 2.0% MEK
peroxide as initiator of the reactions. However, the percentages of
initiator and catalyst can be varied according to the pot-life re-
quired by the preservative. Table 2 reports results obtained at 25 °C
only for all the combinations of 0.5%, 1.0%, 1.5% and 2.0% Cobalt
naphthenate and 0.5%, 1.0%, 1.5% and 2.0% of MEK peroxide.
From the chemical kinetics the half-times of fixation as a function
of the percentages of Cobalt naphthenate and MEK peroxide for
the polyester/Cu preservative can be expressed by the following
three equations:
half-time (minutes) = 180.30 (MEK%) - 0.7394;
for 0.5% Co naphthenate
half-time (minutes) = 147.47 (MEKP%) - 0.5604;
for 1.0% Co naphthenate
half time (minutes) = 86.30 (MEKP%) - 0.2024;
for 2.0% Co naphthenate
Similar equations can also be obtained for the Cu/corn oil and Cu/
rosin systems.
Ultraviolet irradiation of preservative resins at room temperature
The self-polymerization of the preservatives can also be induced by
UV radiation without the necessity of adding Co Naphthenate and
MEK peroxide. The IR band at 780 cm"1 decreases with increasing
reaction time .when the resin is UVMrradiated. The apparent rate
constant, is found to be 1.48 x 10~5/ x mole"1 x sec"1. This is 10
times lower than the apparent rate constant calculated for the
catalysed, non-UV-irradiated preservative at 25 °C (Table 3)s How-
ever, the capability of ultraviolet radiation to induce the reaction at
ambient temperature, without catalysts present, does indicate that
any residual carbon-carbon double bonds in the resin will eventu-
ally continue to react on exposure to the outside environment.
Other fixation mechanisms
As shown, radical-induced fixation occurs and can be measured.
However, other mechanisms can be, and are likely to be, at work
in the fixation of the preservative systems presented. Thus, ionic
fixation mechanisms could also be present. Ionising radiation can
yield active carbocations as well as radicals from aliphatic carbon
chains involving a two-step process: (1st) ionization or electron ex-
pulsion due to absorption of radiant energy and (2nd) fragmenta-
tion of the mixed ion-radical species formed to give a free radical
and a carbocation
CH3 - CH2 - CH2 - CH3 CH3CH2e
If C = C double bonds are present, as they are in wood and in the
resins chosen, both cationic and radical polymerization, and fixa-
tion can occur. Conditions such as the type of solvent, reaction tem-
perature and use of free radical scavengers can favour one or the
other reaction. In this context ionic fixation mechanisms with these
non-toxic preservatives are also likely to be present, although their
extent is unknown.
A. Pizzi: New Approach to Non-Toxic Wood Preservatives. Part 1 259

The polymerization of rosin and resin acids

13
C NMR spectra of resin acids show signals from un-
saturated carbon at many diverse chemical shifts
spread over a range of more than 20 ppm (Newman a
1991) at 148.2; 136.2; 126.4 and 107.8 ppm. Despite
the diversity of chemical shifts for different resin
acids, polymeric resins show only up to 4 signals
across the region associated with unsaturated carbon
(Newman 1991). The simplicity of the NMR spectra
indicates a reasonably uniform type of polymeric link-
age. Wilson et al. (1990) and Anderson et al. (1990)
have proposed a variety of different structures. The
debate over the correct representation of resin acids
polymers is in danger of obscuring the very important
point that the presence of 4 signals (or 3 in abietic
acid) in the 13C NMR spectrum of a rosin is strong evi-
dence of polymerization (Fig. 2).
Self-polymerization by ionic mechanisms has been
identified (Su and Han 1985). Reaction of rosin with
styrene by radical initiation are also already known
and have been studied, although after the initial for- 160 140 120 100 80
mation of the resin acid, or polymerized resin acid, ad-
ducts with styrene further polymerization does not ap- Fig. 2. Region of I3C NMR spectra of rosin and rcsinitc (b) and of
pear to occur (Zhou and Chang 1985). All this indi- polymerized abietic acid (a) indicating the presence of polymerized
material.
cates that there are clear differences in the mode of
action of the rosin soaps in relation to the other types
of wood preservatives. Firstly, both monomeric and Thus, structures such as
polymeric resin acids form Cu2+ soaps, as in rosin a
certain percentage of polymeric material is present.
Secondly the monomeric Cu2+ and the polymeric
Cu2+ soaps are likely to fix by radical initiated reaction
of the carbon-carbon double bonds of the aliphatic
chain segments of wood lignin, as indicated by reac-
tion with styrene as a simple model compound. From
a radical point of view self-polymerization then is
likely to stop once the resin acids monomers and
polymers are fixed to the lignin network. In this re- can be drawn, as well as many others.
spect the Cu soaps of rosin behave differently from
what observed with the unsaturated oils acid and
polyester Cu2+ soaps. Resin acids polymerization
might slowly proceed further, although there is no im-
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