Synthesis and properties of hydrophilic segmented poly(urethanes) based on poly(ethylene glycols) and glycerol monostearate

Poly(urethanes) having the structure of comb-shaped copolymers were synthesized from glycerol monostearate, poly(ethylene glycols) with M _n = 300–6000, and 1,6-hexamethylene diisocyanate. Effects of the molecular mass of segments and of the contents of soft segments and side chains on both the glass transition temperature of the soft segment and on the melting point and the enthalpy of melting of crystalline phases involving soft segments and side chains were studied by DSC and IR spectroscopy. The resulting comb-shaped copolymers were shown to exhibit thermoplastic and hydrophilic behavior. It was demonstrated that the ultimate tensile strength, yield stress, and Young’s modulus of copolymer films increase with an increase in the molecular masses of soft and hard segments with their ratio maintained constant.     

Synthesis and properties of comb-shaped segmented poly(urethanes) based on 1,2-propanediol derivatives

Comb-shaped segmented poly(urethanes) have been synthesized from ethers via the one-step procedure with the use of glycerol monostearate, D,L-3-octadecyloxy-1,2-propanediol, 3-tert-butoxy-1,2-propanediol, 3-benzyloxy-1,2-propanediol, and 1,2-propanediol as chain extenders. The soft segment of poly(urethanes) was derived from macrodiol (poly(tetramethylene glycol) with M _n = 1000), and 1,6-hexamethylene diisocyanate and 4,4′-cyclohexylmethane diisocyanate were used as diisocyanates. The effect of the structure of side chains located at the hard segments on the formation of hydrogen bonds in comb-shaped poly(urethanes) has been studied by IR spectroscopy. On the basis of DSC measurements, the glass transition temperatures of the soft and hard segments and the temperature and enthalpy of melting of the crystalline phase have been estimated and the microphase separation of segments has been assessed. The mechanical characteristics of the polymers under study have been examined.     

Effect of flame retardants on the properties of monolithic and foamed polyurethanes at low temperatures

The dependence of physical and mechanical properties of monolithic and foamed rigid polyurethanes on the content of flame retardants was investigated at 293 and 98 K. The character of the influence of the content of trichloroethyl phosphate on the ultimate tensile elongation and the coefficient of linear thermal expansion for monolithic and foamed polyurethanes at a temperature of 98 K was established. Latvian State Institute of Wood Chemistry, Riga, LV-1006 Latvia. Translated from Mekhanika Kompozitnykh Materialov, Vol. 35, No. 5, pp. 671–676, September–October, 1999.     

Characteristics of Biodegradable Poly(Ester-Urethanes) with Side Chains

Two series of segmented poly(ester-urethanes) (SPEU) have been studied. The flexible segment of SPEU was formed from polycaprolactonediols (PCL diols) with a molecular mass of 600 to 10000 and the rigid one — from a blend of 2.4 and 2.6-toluene diisocyanates (TDI) and a chain extender. The first series of SPEU contained no side branches, whereas in the second series, side branches in the form of long chains of aliphatic structure were present at the rigid segment. The tensile strength of SPEU decreased when the molecular mass of the flexible segment increased from 600 to 2000; in this case, the specimens were of amorphous structure. An increase in the molecular mass of the flexible segment from 2000 to 10000 led to an increase in its degree of crystallinity and in the melting point, fusion enthalpy, tensile strength, yield stress in tension, and packing coefficient of SPEU. The side chains at the rigid segment affected the degree of phase separation insignificantly, but decreased the order of the structure, the glass transition temperature, and strength properties of SPEU, whereas the side chains at the flexible segment reduced its crystallinity.     

Effect of side branches on the properties of cross-linked polyurethanes

Two series of samples of cross-linked polyurethanes: based on diethylene glycol and polypropylene glycol having calculated M_c 1000, were investigated. In synthesis by partial substitution of glycols by fatty acid ester and triethanolamine, long side branches were created in the structure of the polymer. The effect of the mass concentration of these branches on the physicomechanical properties of polyurethanes was evaluated. The different character of the effect of these branches on the properties of two types of polyurethane was demonstrated.Submitted to the Xth International Conference on Mechanics of Composite Materials (Riga, April 20–23, 1998).Latvian State Institute of Wood Chemistry. Riga, LV-1006 Latvia. Translated from Mekhanika Kompozitnykh Materialov, No. 6, pp. 840–844. November–December. 1997.     

Synthesis and properties of poly(ester urethanes) based on cellulose triacetate

Segmented poly(ester urethanes) were synthesized from oligomeric cellulose triacetate diols, poly(caprolactone)diols, and 1,6-hexamethylene diisocyanate. The effects of the molecular mass and structure of soft and hard segments of poly(ester urethanes) on their thermal behavior, mechanical properties, and degradation in aqueous solutions of a phosphate buffer were studied by DSC and IR spectroscopy. The combination of soft segments derived from poly(caprolactone)diols with M = (1.0–3.5) × 10³, hard segments based on depolymerized cellulose triacetate with M = (2–4) × 10³, and 1,6-hexamethylene diisocyanate makes it possible to synthesize poly(ester urethanes) with excellent mechanical characteristics. The degree of crystallinity of these polymers increases with a decrease in the molecular mass of the depolymerized cellulose triacetate block in the hard segment. As the soft segment lengthens, phase separation between domains of soft and hard segments becomes more pronounced. Upon incorporation of poly(ethylene glycol) blocks into the soft segments of poly(ester urethanes), their hydrophobicity is enhanced and biodegradability is accelerated.     

Properties of rigid polyurethane foams filled with milled carbon fibers

The effect of milled carbon fibers of two types (differing in length) on the properties of rigid polyurethane foams in the density range from 50 to 90 kg/m³ is investigated. The coefficient of thermal expansion and properties of the foams in tension and compression as functions of fiber content in them are determined. It is found that the long fibers are more efficient in improving the properties of the foams in their rise direction. The elongation at break of the foams decreases significantly with increasing fiber content.     

Physicomechanical Characteristics of Spray-On Rigid Polyurethane Foams at Normal and Low Temperatures

The effect of processing factors on the inhomogeneity and physicomechanical characteristics of spray-on polyurethane foams is studied. The dependences of the basic characteristics of foam plastics on the apparent density and cell-shape factor are determined. A method is offered for evaluating the effect of the technological surface skin on the tensile characteristics of foam plastics under normal and low temperatures.