Rosin Based Chemicals and Polymers
Rosin Based Chemicals and Polymers
Rosin Based Chemicals and Polymers
Xiaoping Rao
5.1 Introduction
129
Rosin-based Chemicals and Polymers
acids and long chain alkyl groups, as well as aromatic compounds [7]. Rosin acids are
a novel source of hydrophobic groups with a tricyclic hydrophenanthrene structure
that can be used for the synthesis of surfactants with natural origins.
Since the first rosin-based surfactant (rosin acid sodium salt) was reported, the
synthesis and application of rosin-based surfactants have attracted great attention
[8]. Scientists from the United States, Japan, Germany and Russia carried out much
work from the 1920s to the 1960s. After the 1970s, with the rise in labour costs for
tapping in developed countries, the amount of gum rosin reduced greatly in those
countries, they mostly focused on the application of rosin surfactants. However,
from that time on, Chinese scientists have done much work in this field. In recent
years, many new types of surfactants such as gemini and bora surfactants derived
from rosin have been synthesised and their applications investigated. Rosin is an
important natural resource, whose main components are resin acids, and they have
attracted great interest for use in surfactant synthesis and applications because of
their special chemical structures and wide range of applications. There are three
kinds of rosin: gum rosin, wood rosin and tall oil rosin. Gum rosin occupies about
60% of the industrial market, wood rosin about 5% and tall oil rosin about 35%.
The total world annual production volume of rosin has remained at 1.1-1.2 million
tons since the 1990s. The most common pine resin acids have the molecular formula
C20H30O2, [9]. Most pine resin acids belong to three basic skeletal classes: abietane,
pimarane and isopimarane, and labdane. Rosin or modified rosin are widely used as
sizes, adhesives, printing inks, emulsifiers, and these applications account for most
of the rosin used in industry. Pine resin acids have been widely investigated, but the
industrial use of them is low because of their high cost. With the development of science
and technology, pure pine resin acids and their derivatives can be easily separated
from commercial products on a large scale. For example, dehydroabietic acid (DAA)
can be isolated by crystallisation of the 2-aminoethanol salt from disproportionate
rosin, and dehydroabietylamine can be isolated by crystallisation of the acetic acid
salt from commercial disproportionate rosin amine [10]. Rosin and its derivatives are
useful building blocks for the hydrophobic moiety of surfactants since they contain
the tricyclic hydrophenanthrene structure, and hydrophilic groups can be introduced
through reactions of carboxyl groups. The hydrophenanthrene can be obtained in
enantiomerically pure form. Chiral surfactants from rosin can be used as chiral phase
transfer catalysts and chiral separation agents. Surfactants with structures similar to
derivatives of fatty acids, amines and alcohols, can be synthesised from rosin.
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Synthesis and Application of Rosin-Based Surfactants
surfactants can be classified into four groups: cationic, anionic, zwitterionic and
nonionic. Cationic surfactants are those that have a positive charge on their polar
head group. Anionic surfactants are those that have a negative charge on their polar
head group. Zwitterionic surfactants have the potential to have both positive and
negative charges, depending on the environment in which they are placed. Nonionic
surfactants have no charge on their head group. The methods for the synthesis of
different kinds of rosin-based surfactants are summarised below.
Radbil and co-workers used DAA or a mixture of rosin acids to synthesise quaternary
ammonium compounds through chloride intermediates. Chlorides of resin acids
prepared by phosphorus trichloride were esterified with N,N-dimethanolamine. The
corresponding ester quaternary ammonium surfactants (C01-C04) were obtained
after quaternisation with halide [12]. Their synthesis route is shown in Scheme 5.1.
131
Rosin-based Chemicals and Polymers
Under classical conditions, the reactions for synthesising cationic surfactants require
a long reaction time (from 24 to 48 h) to complete the quaternisation reaction,
which results in a lower total yield of the final products and the production of more
byproducts. Microwave activation, as a nonconventional energy source, has become
a very popular and useful technology in organic chemistry [14]. Chemical reactions
brought about by microwave irradiation have gathered momentum in recent years
mainly because of their simplicity, high yield, short time span, and ecofriendly
conditions [15-16].
Gemini surfactants have attracted great interest in recent years. They are made up of
two amphiphilic moieties connected at the head group by a spacer group [17]. Gemini
132
Synthesis and Application of Rosin-Based Surfactants
surfactants have better surface active properties such as remarkably lower critical
micelle concentration (CMC) values than corresponding conventional surfactants of
equal chain length [18]. Jia and co-workers reported that a gemini surfactant with
rosin-based hydrophenanthrene structure (C06) was synthesised by conventional
thermal conditions and microwave irradiation, respectively (Scheme 5.3). The method
of microwave irradiation greatly reduced the reaction time with better yield compared
to the conventional method [19].
Rosin acids can react easily with the epoxy group under mild conditions. Epoxy
chloropropane is the most widely used reagent to react with rosin and its derivatives,
in order to provide a halide or epoxy intermediate to the rosin-based skeleton in an
easy way. The intermediate can react with a tertiary amine in a standard procedure
to prepare quaternary ammonium compounds. A halide intermediate can be formed
from DAA and epoxy chloropropane (Scheme 5.4), after a standard quaternisation
procedure to prepare quaternary ammonium compounds (C07) [20]. Wei and co-
workers reported bora type bis-quaternary ammonium cationic surfactants (C08-C09)
which were synthesised from acrylic-modified rosin as shown in Scheme 5.5 [21]. Chen
and co-workers reported the synthesis of a new sulfodehydroabietic acid based on a
bis-quaternary ammonium cationic surfactant (C10), which was synthesised by the
sulfonation of DAA, followed by reaction with epoxy chloropropane and triethylamine
(Scheme 5.6) [22]. Hu and co-workers reported the synthesis of a new gemini surfactant
CsH2s-α, ω-Bis (dehydroabietylhydroxypropyltetra- methylethyldiammonium) chloride
(C11) through an epoxy chloropropane intermediate (Scheme 5.7) [23].
133
Rosin-based Chemicals and Polymers
134
Synthesis and Application of Rosin-Based Surfactants
Rosin acid reacted with epoxy chloropropane in alkaline conditions to form the
corresponding ester with an epoxy group, which reacted with amine to form a
tertiary amine, and then reacted with halide to form quaternary ammonium salt
cationic surfactants (C12-C13, Scheme 5.8). Rosin acid reacted with an epoxy group
quaternary ammonium salt to form cationic surfactants directly (C14) (Scheme 5.9)
[20].
135
Rosin-based Chemicals and Polymers
The most widely used starting materials for the synthesis of rosin-based quaternary
ammonium compounds are rosin amine or dehydroabietylamine [24]. Rosin amine
or dehydroabietylamine can be used as starting materials to prepare tertiary amine in
the presence of formaldehyde and formic acid, and then the rosin based quaternary
ammonium salts can be prepared in a standard procedure called quaternisation.
N,N-Dimethyldehydroabietylamine (DMDHA) is a very important intermediate for
the synthesis of rosin-based cationic surfactants. There are two methods to synthesise
DMDHA. It can be synthesised under mild conditions, in which dehydroabietylamine,
formic acid and formaldehyde solution are refluxed together at a temperature of 65 ℃
for about 5-7 h, which gives a yield of 70-80%. The other method is hydrogenation
by formaldehyde under pressure, which gives a yield of 89-94%. Ordinarily the first
method is widely used because of the mild reaction conditions [25-27].
136
Synthesis and Application of Rosin-Based Surfactants
137
Rosin-based Chemicals and Polymers
Quaternary ammonium salts can also be introduced into the rosin skeleton directly.
Cai and co-workers reported the direct synthesis of 3-dehydroabietylamino-2-
hydroxypropyl trimethyl ammonium chloride (C32) from dehydroabietylamine and
3-chloro-2-hydroxypropyl trimethyl ammonium chloride in the presence of an acid-
binding agent loaded on to alumina (Scheme 5.14) [32].
Anionic surfactants are the most widely used class of surfactants in industry. There are
four kinds of hydrophilic groups (carboxylates, sulfates, sulfonates and phosphates)
for rosin-based anionic surfactants, with the tricyclic hydrophenanthrene structure
as the hydrophobic group. A general formula may be ascribed to rosin based
anionic surfactants: Carboxylate: RCOO-X; Sulfate: ROSO2- X; Sulfonate: RSO3- X;
Phosphate: ROPO (OH) O-X; R is the rosin-based tricyclic hydrophenanthrene group
and X is Na or K.
Carboxylates were the earliest rosin-based surfactants. They consist of rosin soaps,
e.g., sodium, potassium or calcium rosin soaps (A01) (Scheme 5.15). The rosin is
saponified by addition of a base so that it becomes soluble in water. Since the first
report of rosin soap as an anionic surfactant by Strassbury in 1919, these compounds
have been widely used as paper sizing agents and in rubber production [20]. Rosin
acids can be modified into multicarboxylic acids by the Diels-Alder addition
reaction. Wang and co-workers reported that a new type of chiral surfactant, sodium
maleopimaric acid (SMA) (A02), was synthesised from rosin and maleic anhydride
adduct compounds and then reacted with sodium hydroxide solution by the method
shown in Scheme 5.16 [33]. Compared with rosin soap, SMA has three carboxylates
in the tricyclic structure.
138
Synthesis and Application of Rosin-Based Surfactants
139
Rosin-based Chemicals and Polymers
Sulfonate surfactants contain a sulfur atom which is directly attached to the carbon
atom of the alkyl group, giving the molecule stability against hydrolysis compared
with the sulfate surfactants. There are three methods to introduce the sulfonate group
into rosin and its derivatives: the first one is to sulfonate the hydroxyl groups directly
with sulfonating agent such as concentrated sulfuric acid, the second is to add sulfate
salt to the double bonds of rosin derivatives and the third one is to react the rosin
derivative with a functional group containing a sulfonate group. DAA has an aromatic
ring, which provides another group for preparing sulfonate anionic surfactants. Chen
and co-workers reported a new unsymmetrical bora form surfactant, (disodium
sulfodehydroabietate [A06]) which was synthesised by sulfonation of dehydroabietic
acid followed by neutralisation (Scheme 5.18) [35].
The most widely studied of rosin-based anionic surfactants are sulfonate salts, which
are usually prepared by reacting rosin acid or rosin amine with alcohol. The terminal
hydroxyl group is then esterified with maleic anhydride (MA), followed by the
addition of sulfate to the double bond to form the corresponding sulfonate anionic
surfactants (Scheme 5.19). Rosin, rosin amine or dehydroabietylamine, rosin hydroxyl
ethyl amide and acrylic rosin can be ethoxylated by epoxy and the terminal hydroxyl
group can be esterified by MA, after addition of sulfate to the double bond to form
corresponding sulfonate anionic surfactants (A07-A11) [36, 37].
140
Synthesis and Application of Rosin-Based Surfactants
141
Rosin-based Chemicals and Polymers
Rosin acids can be changed into acid chlorides, salts and amines, which greatly improve
the reactivity. The chlorides, salts and amines can be reacted with a sulphonate-
containing alcohol (Scheme 5.22) to form sulfonate surfactants under ambient
conditions (A14-A16). Jia and co-workers reported using dehydroabietylamine, α,
ω-dibromoalkane and sodium 2-bromoethylsulfonate as raw materials (Scheme 5.23)
for synthesising new gemini anionic surfactants (N, N′-Sodium-2-diethylsulfonate-N,
N′-didehydroabietate- a ω-diamines [A17]). [40]
142
Synthesis and Application of Rosin-Based Surfactants
Alkyl phosphates are made by treating the ester ethoxylates of rosin with a
phosphorylating agent, usually phosphorous pentoxide. The reaction yields a mixture
of mono- and diesters of phosphoric acid. Wang and co-workers reported (Scheme
5.24) that a phosphate anionic surfactant was synthesised by phosphorylating
polyoxyethylene abietate (A18) using phsphorus pentoxide as the phosphorylating.
Polyoxyethylene abietate was prepared from disproportionated rosin and ethylene
oxide [41].
143
Rosin-based Chemicals and Polymers
When a single surfactant molecule exhibits both anionic and cationic dissociations
it is called zwitterionic [42]. The main characteristic of zwitterionic surfactants is
their dependence on the pH value of the solution in which they are dissolved. In
acid solutions, the molecule acquires a positive charge and behaves like a cationic
surfactant, whereas in alkaline solutions it becomes negatively-charged and behaves
like an anionic one [43].
Rosin-based amino acids are widely investigated zwitterionic surfactants. Rosin acid
and dehydroabietylamine can be used as raw materials for the synthesis (Scheme 5.26)
of this kind of surfactant (Z04-Z08). Rosin acid chloride can react with an amino
acid to form zwitterionic surfactants. This reaction can take place with different
kind of amino acids to form different kinds of zwitterionic surfactants. Liu and co-
workers reported that abietinylglycine was synthesised by the reaction of glycine
and abietic chloride in a water/acetone system and the reaction was accelerated by
a phase transfer catalyst. Benzyl trimethylammonium bromide was a good catalyst
and pyridine was a good base for the reaction [45]. Fang and co-workers reported
using disproportionated rosin and sarcosine as the main starting materials to prepare
disproportionated rosinoyl sarcosine through a chloride intermediate in the same
way [46, 47].
144
Synthesis and Application of Rosin-Based Surfactants
145
Rosin-based Chemicals and Polymers
146
Synthesis and Application of Rosin-Based Surfactants
The most common nonionic surfactants are those based on ethylene oxide and are
prepared by the addition of ethylene oxide to carboxylic acid, primary or secondary
amines, alcohol or monoalkanolamide, or by the reaction of rosin acid with
polyethylene glycol (PEG) (Scheme 5.30) with different molecular weights to form
surfactants (N01-N06) [20].
147
Rosin-based Chemicals and Polymers
148
Synthesis and Application of Rosin-Based Surfactants
The hydroxyl group of rosin ester can also be esterified. Wei and co-workers reported
the synthesis of hydrogenated rosin-polyethylene glycol ester (N07) under microwave
irradiation (Scheme 5.31). The reaction time using microwave irradiation was shorter
than when the conventional heating method was used [51]. Then, the target product
hydrogenated rosin-polyethylene glycol-citric acid ester (N08) (Scheme 5.32) was
prepared by further esterification of the intermediate with citric acid. Wei and co-
workers reported the preparation of disproportionated rosin-polyethylene glycol ester
using the same method [52].
Sugar is a green, natural hydrophilic building block for surfactants and for this
reason, surfactants based on sugar are attracting a great deal of attention. Glucose
and sucrose were introduced into the skeleton of rosin by different kinds of reaction.
Xu and co-workers reported that glucose dehydroabietate (N09) was synthesised by
O-acylation of dehydroabietyl chloride with glucose in the presence of an ionic liquid
1-butyl-3-methylimidazolium bromide as a green reaction solvent (Scheme 5.33). The
catalyst could be recycled and used for three times [53]. Cen and co-workers reported
149
Rosin-based Chemicals and Polymers
that the acid chloride of rosin reacted with sucrose to form the corresponding ester
(N10) (Scheme 5.34) [54]. They also reported using rosin as the raw material for
the synthesis of rosin glycide diethanolamine propenoic acid sucrose ester (N11)
(Scheme 5.35) [55]. Mehltretter and co-workers reported that rosin amine reacted
with gluconolactone to form the corresponding glucose rosin nonionic surfactant
(N12) (Scheme 5.36) [56].
150
Synthesis and Application of Rosin-Based Surfactants
151
Rosin-based Chemicals and Polymers
Specialty surfactants such as silicone surfactants can lower the surface tension of water
to below 20 mN/m. Silicone surfactants are sometimes referred to as ‘superwetters’
as they cause enhanced wetting and spreading in aqueous solution [59]. However,
they are much more expensive than conventional surfactants and are only used for
specific applications for which low surface tension is a desirable property. Silicone-
modified rosin-based surfactants (N15) can be synthesised from rosin acid chloride
(Scheme 5.39) [20].
Azacrown ethers are new functional compounds. They have specific surface activities,
catalytic activities, complex selectivity and good adsorption properties for many heavy
or precious metal ions. Yang and co-workers [60] reported the synthesis of three
chiral azacrown ethers from rosin: N-dehydroabietyl monoaza-15-crown-5 (N16),
N-dehydroabietyl monoaza-18-crown-6 (N17) and N-nor-dehydroabietyl monoaza-
12-crown-4 (N18) (Scheme 5.40). Dehydroabietylamine and nor-dehydroabietylamine
can react with ether diiodide to form the corresponding azacrown ethers. Hydroxyl
derivatives of rosin reacted with tosylate to form the corresponding azacrown ethers.
The azacrown ethers can be employed as phase transfer catalysts in the asymmetric
Michael addition of 2-nitropropane to chalcone.
152
Synthesis and Application of Rosin-Based Surfactants
153
Rosin-based Chemicals and Polymers
Table 5.1 lists some of the physical properties of cationic rosin-based surfactants.
Their surface activities were compared with that of the widely used cationic surfactant,
benzalkonium bromide. The CMC values of most cationic quaternary ammonium
compounds such as C01-C04 are between 10-4-10-3 mol/L with δCMC values between
32-50 mN/m. However, the rosin-based cationic gemini surfactants, such as C06,
C25-C28, exhibited lower CMC values, which were near 10-5 mol/L with δCMC values
between 23-31 mN/m. Gemini surfactants had a low δCMC and CMC value, and the
CMC of these was about two orders of magnitude lower than the corresponding
conventional surfactants with the same alkyl chain length.
δCMC(25
CMC FP(0/5min) EP
Surfactants °C) KP (°C)
(mol/L) mm (Benzene)
(mN/m)
C01 35-36 5×10-3 — — —
C05 — 7.85×10-3 — 16 s —
154
Synthesis and Application of Rosin-Based Surfactants
Table 5.2 shows the physical properties of some rosin-based anionic surfactants, and
their surface activities were compared with that of widely used anionic surfactant
of sodium dodecyl sulfate (K12) and alcohol ether sulfate (AES). The δCMC of most
anionic surfactants were between 24 and 40, and their CMC values were between
10-4-10-3 mol/L. Rosin-based anionic gemini surfactants also showed better CMC
and δCMC values than conventional ones.
155
Rosin-based Chemicals and Polymers
Table 5.3 shows the physical properties of some rosin based zwitterionic surfactants.
The δCMC of most zwitterionic surfactants were between 24 and 40, and their CMC
values were near 10-3 mol/L.
156
Synthesis and Application of Rosin-Based Surfactants
Table 5.4 shows the physical properties of some rosin based nonionic surfactants.
The δCMC of most anionic surfactants are near 40, and their CMC values are near
10-3 mol/L. Rosin-based nonionic surfactants with different degree of polymerisation
were investigated in detail and the results showed that their CMC values were near
10-4 mol/L and the δCMC values were between 32-40 mN/m.
Persson and co-workers investigated [61] the phase behaviour of two rosin-
based nonionic surfactants, polyoxyethy1ene dehydroabietates (DeHAb(EtO))
with polyoxyethylene chains of 11 and 22, in water and decanol system (Figure
5.1). DeHAb(EtO)11 is completely miscible with water but has a low capacity for
solubilisation of decanol. However, at DeHAb(EtO)22 surfactant concentrations of
0-25%, the maximum solubilisation capacity for decanol represents a nearly constant
ratio between the amount of solubilisate and surfactant. The results showed that
the two rosin-based surfactants behave similarly to nonionic surfactants with a
hydrophobic aliphatic carbon chain and a polyethylene oxide chain as the hydrophilic
group. However, the acyclic surfactant has a good solubilising capacity for most
157
Rosin-based Chemicals and Polymers
158
Synthesis and Application of Rosin-Based Surfactants
0 100 0 100
25 ˚C 25 ˚C
r
we
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te
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wa
wa
igh
igh
%
%
t%
t%
t
t
igh
igh
de
de
we
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c
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an
an
L
ol
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L
LC
LC
100 0 100 0
0 weight % DeHAb(E10) 100 0 weight % DeHAb(E10) 100
11 22
Jiang and co-workers [62] reported that critical aggregation numbers of micelles
(N) of rosin-modified quaternary ammonium gemini surfactants (C25-C27) were
determined by a steady-state fluorescence probe method. The results showed that N
increased linearly with the increase of the surfactant concentration in a range of 5-15
times CMC and critical aggregation numbers of micelle (Nm) can be extrapolated
from the N—C curve, which were 10, 19, and 20 for C25, C26 and C27 respectively.
5.4 Applications
Rosin acids are tacky solids at room temperature. Saponify the rosin by addition
of base so that it becomes soluble in water and it then can be added effectively to a
paper machine. Different industries use gum rosin in varying amounts as is indicated
in Figure 5.2. Soap production, paper making and the synthetic rubber industry
consume large amounts of rosin [63].
159
Rosin-based Chemicals and Polymers
Coating 12.9%
Soap 43.9%
Figure 5.2 Gun rosin usage in industry, the data adapted from reference [63]
Most rosin soaps have water-loving carboxylate groups, and the remainder of the
rosin molecule has a water-hating hydrocarbon group. The rosin soap exists as
micelles in solution, and the groups of soap molecules associate with each other so
that the water-hating parts face each other to avoid contact with water. Aluminum
compounds are needed for paper making furnish. Aluminum ions react with the
carboxylate groups in the rosin, which causes the rosin to precipitate on to the fibre
surface. The recommended pH conditions for rosin soap sizing are dictated by the
effect of pH on the predominant species of the aluminum ions. Low pH conditions
favour the presence of trivalent aluminum, a hydrated form of Al3+. This is the species
that appears to be most useful for the retention and setting of rosin soap size [64].
Rosin soaps are designed for use as an emulsifier in the polymerisation of styrene-
butadiene rubber and other synthetic rubbers. It was used for the polymerisation
of styrene-butadiene rubber emulsifiers. When dispersed in the aqueous phase of
the monomer emulsion they facilitate micelle formation, thereby forming stable
monomers. Rosin calcium soap is used in paints. Lead, cobalt and manganese have
been used traditionally as driers in these paints.
160
Synthesis and Application of Rosin-Based Surfactants
through the binding of their ammonium cationic groups to anionic sites in the
outer tissue layers of bacteria [65]. As a result of the combination of their tricyclic
hydrophenanthrene structure and quaternary ammonium group, rosin-based cationic
surfactants exhibit good antibacterial activity.
161
Rosin-based Chemicals and Polymers
140
C32
120 Ofloxacin
Bromo-geramium
100
80
MIC (µg/mL)
60
40
20
0
S. aueus S. epidemidis C. perfringens K. pneumonice E. coli P. aeruginosa S. almonella
Bacterium
162
Synthesis and Application of Rosin-Based Surfactants
The majority of uses of rosin-based surfactants are in paper sizing agent, as a rubber
emulsifier and as antibacterial agents. The uses of diterpene resin acids as convenient
chiral pools for the synthesis of chiral ligands suitable for metallocomplex catalysts
of asymmetric reactions have been studied [68] but, so far, there have been few
applications in this field. The use of pine resin acids as chiral pools would also be
useful for the preparation of chiral surfactants.
163
Rosin-based Chemicals and Polymers
Pan and co-workers reported [29] using four novel chiral quaternary ammonium
salts (C21-C24) synthesised from dehydroabietylamine as phase transfer catalysts in
asymmetric epoxidation reactions of chalcone (Scheme 5.41). The results indicated
that chalcone cannot be oxidised by sodium chlorate or hydrogen peroxide without
catalysts in several days. However the reaction could occur in the presence of a
rosin-based chiral catalyst. The structure and amount of catalyst affected the reaction
greatly. The catalyst that contained benzene groups at the head greatly accerated
the reaction procedure, with higher selectivity compared to a catalyst with an alkyl
group. They afforded the corresponding epoxides in high yields and up to 20%
enantiomeric excess (ee) [69].
Yang and co-workers used [60] three chiral azacrown ethers, i.e., N-dehyroabietyl
monoaza-1,5-crown-5, N-dehyroabietyl monoaza-1,8-crown-6 and N-degrading-
dehyroabietyl monoaza-12-crown-4 [N16-N18] synthesised from rosin as phase
transfer catalysts in the asymmetric Michael addition of 2-nitropropane to chalcone
(Scheme 5.42). This afforded the corresponding Michael addition products with up
to 35% ee value. Three kinds of rosin-based chiral azacrown ethers can catalyse
chalcone Michael addition reactions. The yield is about 43-51% and the ee value
reached 35% with the best catalyst activity. The structure of the azacrown ether greatly
affected the selectivity of the catalyst reactions. These chiral azacrown ethers can also
catalyse epoxidation reactions of chalcone, and the yield of products reached 47-69%.
However, these catalysts almost have no selectivity to form enantiomeric products.
164
Synthesis and Application of Rosin-Based Surfactants
Because there are many chiral carbon atoms in the pine resin acids and their
derivatives, they have been widely used in the separation technology. Pine resin acids
and amines are used as chiral reagents for the resolution of isomers of biological
compounds. For example, dehydroabietic acid is used as a reagent for separating
chiral amines and dehydroabietylamine is used as a reagent to separate chiral acids.
These separation reactions usually depend on salt formation reactions, and according
to their solubility in organic solvents, resolution of the biological isomers can be
obtained by recrystallisation. With the development of separation technology, micellar
electrokinetic chromatography (MEKC), as an electrokinetic separation technique
[70], has become one of the most popular techniques in the field of separation science
due to its high resolving power and capability of separating both ionic and neutral
compounds. One of the attractive applications of MEKC is enantiomer separation
[71]. In MEKC, chiral surfactants have been used as a pseudostationary phase for
chiral separation. Rosin is a naturally occurring enantiomeric diterpenic acid, which
is an excellent starting material for preparing chiral surfactants because of its wide
availability and special stereostructure.
Wang and co-workers reported [33] a new type of anionic chiral surfactant (SMA,
[A02, see Scheme 5.16]), which was used for the enantioselective MEKC separation of
amino acid enantiomers derivatised with naphthalene-2,3- dicarboxaldehyde (NDA-
d/l-AA). Under the conditions selected, two pairs of tested amino acid enantiomers,
including NDA-d/l-trptophan and NDA-d/l-kynurenine were resolved. On the other
hand, SMA showed high aqueous solubility and low CMC, which simplified the
MEKC methodology, and avoided the use of a comicellar phase system and organic
solvents for chiral separation [33].
Zhao and co-workers reported [49] a new type of zwitterionic chiral surfactant,
DHAMAP, (Z10, see Scheme 5.28) which was used to perform chiral separation
of d/l-amino acids by capillary electrophoresis (CE). Six pairs of tested amino acids
enantiomers including NDA-d/l-tryptophan (NDA-d/l-Trp), NDA-d/l-phenylalanine
(NDA-d/l-Phen), NDA-d/l-kynurenine (NDA-d/l-Kyn), NDA-d/l-β-phenylalanine
(NDA-d/l-β-Phen), NDA-d/l-4-methylphenylalanine (NDA-d/l-4-M-Phe) and NDA-
d/l-arginine were well-resolved (Figure 5.4). All compounds were fully separated
by using a chiral running buffer consisting of a rosin-based surfactant DHAMAP.
However, separation was not obtained if the running buffer did not contain DHAMAP.
DHAMAP is an amphoteric chiral surfactant; alterations of buffer pH can affect
the charge on the analyte and the chiral pseudophase, thus influencing the chiral
separation.
165
Rosin-based Chemicals and Polymers
10
L-β-phe
D-Kyn
D-Trp
L-Kyn
8
D-β-phe
L-Trp
6
4
2
mAU
0
–2
–4
–6
–8
0 5 10 15 20 25
t/min
The ability of surfactants to self-assemble into well-defined structures has been taken
advantage of for the design and synthesis of inorganic materials with nanosized
dimensions [72]. This approach to nanomaterials preparation has triggered substantial
interest both in the surface chemistry and the materials chemistry community. In
the previous research, surfactants have been used as templates in the synthesis of
nanoinorganic powder materials, nanostructured materials, nanocomposite materials
and Langmuir-Blodgett films. The size, charge, and shape of the surfactant are
important structure-determining parameters in the synthesis of the materials.
166
Synthesis and Application of Rosin-Based Surfactants
167
Rosin-based Chemicals and Polymers
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