1070-4272/04/7710-1715 C 2004 MAIK [Nauka/Interperiodica]
Russian Journal of Applied Chemistry, Vol. 77, No. 10, 2004, pp. 1715!1720. Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 10, 2004,
Original Russian Text Copyright + 2004 by Bondarenko, Khokhlova, Orlova, Tuzhikov.
AND POLYMERIC MATERIALS
Synthesis of Polyurethanes with B,P-containing Polyols
S. N. Bondarenko, T. V. Khokhlova, S. A. Orlova, and O. I. Tuzhikov
Volgograd State Technical University, Volgograd, Russia
Volzhskii Polytechnic Institute, Volzhskii, Volgograd oblast, Russia
Received July 9, 2004
Abstract-Polyurethanes were prepared from diphenylmethane-4,4`-diisocyanate, poly(tetramethylene ether)
glycol, and B, P-containing polyols. The structure and properties of these polyurethanes were studied in rela-
tion to the synthesis conditions, including the functional group ratio and temperature. The heat resistance
of the polyurethanes was evaluated.
Preparation of polymers containing boron atoms in
the macromolecule was discussed in an analytical re-
view ; in particular, methods for preparing polyure-
thanes containing carborane and borinane structures
were considered. Such polymers are synthesized from
low-molecular-weight carborane-containing ethers and
esters and aliphatic diisocyanates, or from carboranyl-
ene diisocyanates and various diols.
However, factors that control the lengthening of the
polymeric chain and properties of the polymers pre-
pared using oligomeric chain-lengthening organometal-
lic agents were not analyzed comprehensively in .
Our goal was to reveal a relationship between the
molecular parameters of the starting polyols contain-
ing borate and phosphonate groups, on the one hand,
and the properties of polyurethanes prepared from
these polyols, on the other.
Polyurethanes were prepared by a two-step proce-
dure. The reaction of a twofold excess of diphenyl-
methane-4,4`-diisocyanate (DMI) with poly(tetra-
methylene ether) glycol (PTMEG) yielded a macro-
molecular diisocyanate (MDC). The resulting MDC
was brought into the reaction with a B,P-containing
polyol (BPP) as a chain-lengthening agent.
Polyurethanes and MDC were prepared in a high-
speed (1400 rpm) temperature-controlled mixer in an
argon flow in dimethylformamide (DMF).
B,P-Containing polyols BPP-1, BPP-2, BPP-3, and
BPP-4 were prepared according to  by reactions of
glycols (ethylene glycol, diethylene glycol, glycerol,
and 1,4-butanediol, respectively) with the phosphorus-
containing oligomer . The reaction occurs on heat-
ing of the equimolar amounts of the reactants under
Ar at 4533463 K without a catalyst for 5+1h.
The reaction products are viscous liquids with the
color varying from light yellow to brown. The main
physicochemical parameters of BPPs are listed in
The structure of the BPPs obtained was confirmed
P NMR and by IR spectroscopy. The
Table 1. Physicochemical properties of B, P-containing polyols
B, P-Con- ³³³ ³³Content ³ P content, %
³ ³ ³ ³ ³ ÃÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄtaining ³ n
³ n,St ³ r
³ MW ³ of OH groups, ³
polyol ³³³ ³³%³found ³ calculated
BPP-1 ³ 1.4748 ³ 32.7 ³ 1.2573 ³ 820 ³ 6.6 ³ 29.4 ³ 28.9
BPP-2 ³ 1.4730 ³ 30.1 ³ 1.8839 ³ 910 ³ 6.2 ³ 26.8 ³ 26.2
BPP-3 ³ 1.4842 ³ 33.8 ³ 1.4486 ³ 890 ³ 8.2 ³ 27.8 ³ 27.3
BPP-4 ³ 1.4797 ³ 31.3 ³ 1.6243 ³ 880 ³ 6.6 ³ 28.1 ³ 28.7