Russian Journal of Applied Chemistry, 2011, Vol. 84, No. 2, pp. 325−328.
Pleiades Publishing, Ltd., 2011.
Original Russian Text © L.M. Popova, Yu.A. Dmitrieva, S.V. Vershilov, 2011, published in Zhurnal Prikladnoi Khimii, 2011, Vol. 84, No. 2, pp. 329−332.
Esteriﬁ cation of Polyﬂ uoroalkyl Alcohols with Tall Oil Rosin
L. M. Popova
, Yu. A. Dmitrieva
, and S. V. Vershilov
St. Petersburg State Technological University of Vegetable Polymers, St. Petersburg, Russia
Lebedev Research Institute of Synthetic Rubber, Federal State Unitary Enterprise, St. Petersburg, Russia
Received July 15, 2010
Abstract—Acid-catalyzed nonsolvent esteriﬁ cation of 1H,1H,5H-perﬂ uoropentan-1-ol, 1H,1H,7H-perﬂ uoroheptan-
1-ol, and 1H,1H,9H-perﬂ uorononan-1-ol with tall oil rosin was studied.
Tall oil rosin esters have been known for long time
[1–3]; they are extensively applied in oil processing and
paint and varnish industries, as well as for manufacturing
offset paints and melt adhesives and imparting long-
lasting qualities to fragrance. Some of these esters are
part of medicinal preparations, and those exhibiting
surface activity are used as emulsiﬁ ers.
There exist published data on synthesis of
polyﬂ uorinated tall oil rosin esters. For example,
chromatographic/mass-spectrometric analyses of
pentaﬂ uorobenzyl esters of resin acids are widely
practiced by foreign countries when assessing the
environmental safety of wastewater generated by
paper and pulp industry [4–6]. Earlier, triﬂ uoroethanol
and telomeric alcohol (n = 1–4) abietates and
dehydroabietates were synthesized by the reaction
of resin acids , abietoacetic acid anhydride 
with alcohols in the presence of sulfuric acid or the
corresponding acid chlorides with sodium alcoholates
Here, we continue our studies aimed to develop
high-performance ﬂ uorinated surfactants [7–9] by
carrying out acid-catalyzed reactions of tall oil rosin
with telomeric alcohols: 1H,1H,5H-perﬂ uoropentan-1-
ol (n = 2) (IIa), 1H,1H,7H-perﬂ uoroheptan-1-ol (n = 3)
(IIb), and 1H,1H,9H-perﬂ uorononan-1-ol (n = 4) (IIc).
The synthetic route we chose for synthesis of
polyﬂ uoroalkyl esters of tall oil rosin is based on the
use of commercially available chemicals: tall oil rosin,
a large-tonnage cheap byproduct in sulfate cooking of
cellulose, and telomeric alcohols (n = 2–4).
Esteriﬁ cation of polyﬂ uoroalkyl alcohols (IIa–IIc)
with tall oil rosin (I) followed the procedure identical to
that described in , except for the use of concentrated
(10–15% of the weight of the initial tall oil
resin) as catalyst instead of p-toluenesulfonic acid. The
reaction was carried out at the equimolar ratio of the
reactants without a solvent at 150–200°С for 5–6 h.
The course of the reaction was monitored by thin-layer
chromatography (TLC), till the chromatographic plate
contained negligible amounts of the initial tall oil rosin.
Upon completion of the process the reaction mixture
was dissolved in 50 ml of diethyl ether and successively
washed with 5% sodium bicarbonate solution and
distilled water until the wash water had neutral pH. After
this the ether solution was dried with calcined sodium
sulfate, the solvent was distilled off, and the residue was
kept in a vacuum over Р
. The resulting brown resins
IIIa–IIIc were obtained in the 87–90% yield (Table 1).
The composition and structure of the synthesized
compounds were proven by analytical and spectral
The composition and structure of the resulting
products IIIa–IIIc were also conﬁ rmed by the UV, IR,
F NMR spectroscopic data (Table 2).
The characteristic maxima in the UV absorption