1070-4272/02/7510-1715 $27.00 C 2002 MAIK [Nauka/Interperiodica]
Russian Journal of Applied Chemistry, Vol. 75, No. 10, 2002, pp. 1715!1717. Translated from Zhurnal Prikladnoi Khimii, Vol. 75, No. 10, 2002,
Original Russian Text Copyright + 2002 by Storozhakova, Efanova, Rakhimov.
Reactions of Polyfluorinated Telomeric Alcohols
N. A. Storozhakova, E. Yu. Efanova, and A. I. Rakhimov
Volgograd State Technical University, Volgograd, Russia
Institute of Chemical Problems of Ecology, Russian Academy of Natural Sciences, Volgograd, Russia
Received January 17, 2002
Abstract-The possibility of preparing fluorinated oligomeric derivatives of e-aminocaproic acid by reaction
of polyfluorinated telomeric alcohols H(CF
OH (n =134) with e-caprolactam under conditions
of homogeneous catalysis (triethylamine, dimethylformamide) was examined. The thermal stability of
the oligomers was studied in relation to the fluorine content.
Reactions of e-caprolactam with saturated mono-
hydric alcohols have been studied previously under
conditions of heterogeneous (lead oxide, lead powder,
zinc powder ) and homogeneous (triethylamine,
TEA; dimethylformamide, DMF ) catalysis. The
resulting oligomeric esters are of interest as matrices
for preparing substances with biomedical activity .
With fluorinated alkoxy groups, these compounds
show promise for preparing materials with decreased
combustibility , enhanced resistance to aggressive
media and organic solvents , and decreased fric-
tion coefficient .
The goal of this study was to prepare fluorinated
oligomers by reaction of e-caprolactam with poly-
fluorinated telomeric alcohols of the general formula
OH, where n = 1 (PFA1), 2 (PFA2),
3 (PFA3), and 4 (PFA4), and to analyze their physico-
The reaction of e-caprolactam with polyfluorinated
alcohols was performed at a molar ratio e-caprolac-
tam : alcohol = 1 : 1.2 in the presence of catalytic
amounts (0.05 mol) of lead oxide, TEA, or DMF at
high temperature (260oC). At lower temperatures, the
oligomer yield is low.
Kinetic experiments were performed with PFA2;
we monitored the amounts of unchanged e-caprolac-
Reported at the 3rd International Conference [Chemistry,
Technology, and Application of Fluoro Compounds,] St. Pe-
tersburg, June 639, 2001.
tam (as described in ) and polyfluorinated alcohol,
which was isolated by vacuum distillation. Also, we
determined the yield of the oligomer after its isolation
by filtration. The oligomer was recrystallized from
The structure of the oligomer was determined by
IR and NMR spectroscopy. The IR spectra were re-
corded with a Specord M82 spectrometer (mulls in
mineral oil, NaCl or KBr cells). The
H NMR spectra
were taken on a Tesla BS487 spectrometer (100 MHz,
internal reference HMDS, solvent dimethyl sulfoxide).
The thermal stability of polyfluorinated oligomers
was studied with an MOM derivatograph (Hungary).
Samples were heated to 500oC over a period of
Polyfluorinated telomeric alcohols react with the
lactam in the presence of DMF to give esters of alco-
hols and e-aminocaproic acid oligomers:
OH + HN(CH
where n =134, m =2,3.
The yield of polyfluorinated oligomers increases
with decreasing length of the fluorocarbon chain,
being 32341% with PFA1 and PFA2 and 10313%
with PFA3 and PFA4. It is convenient to purify the
oligomers by recrystallization from hot acetic acid.
Trimers precipitate upon cooling; their melting points
(oC) are as follows: PFA1, 192; PFA2, 204. Dimers