Phase Segregation of Polyester Based-Polyurethanes

Abstract

ABSTRACT:Polyester based polyurethanes were synthesized from 4,4'-methylene bis(phenyl isocyanate) (MDI) with 1,4-butanediol as a chain extender and low molecular weight polyester-diol as a soft segment. Four polyesters were used in the synthesis of polyurethanes. Two of the polyesters were synthesized from monomers with even carbon atoms, i.e., adipic acid with 1,6-hexanediol (polyester-6-6) and adipic acid with 1,4-butanediol (polyester-6-4). The other two polyesters were synthesized from monomers with odd carbon atoms, i.e., pimelic acid with 1,5-pentanediol (polyester-7-5) and 1,5-pentanedioic acid with I ,5-pentanediol (polyester-5-5). The effects of compatibility between soft-and hard-segments and the chemical structures of polyesters on the phase segregation of soft-and hard-segments were studied by DSC and FT-IR.KEY WORDS Polyurethane I Differential Scanning Calorimetry I Fourier Transform Infrared Spectroscopy I Phase Segregation IThe polyester based urethanes consist of an aromatic diisocyanate with a glycol chain extender as the hard segment and a low molecular weight polyester as the soft segment. They are considered to be linear segmented block copolymer, made up of alternating hard and soft block segments. It has been reported that soft-and hard-segmental phase segregation of polyurethanes is strongly controlled by the compatibility of these two segments and the chain mobility of hard segments inside the soft domain. 1 • 2 Polyurethane of structure -[(0 = C)NH(CH2)nNH(C=O)O(CH 2 )mOJ-has been shown that when "n" and "m" are even the fit of each hydrogen donor group (NH) to each electron donor group (C=O) should be relatively easy, whereas when "n" or "m" is odd the fit should not be perfect. 3 Thus, in an irregular structure (n or m is odd and fit is poor) not all groups should participate in hydrogen bonding, inter-molecular attractions should be weaker, and the melting point should be lower. It is known that the "zigzag" structure of polyester affects the geometric fit of polymer molecules and thus the crystallization behavior of polyesters.In the present work, we studied the soft-and hardsegment phase segregation behavior of polyester basedpolyurethanes with two of the polyesters were synthesized from monomers with even carbon atoms, i.e., adipic acid with 1,6-hexanediol (polyeester-6-6) and adipic acid with 1,4-butanediol (polyester-6-4) and the other two polyesters were synthesized from monomers with odd carbon atoms, i.e., pimelic acid with 1 ,5-pentanediol (polyester-7-5) and 1,5-pentanoic diacid with 1,5-pentanediol (polyester-5-5). Attempt has been made to correlate the polyurethane morphology with the polyester "zigzag" structures, the crystallinity of polyester soft segments, NH to C = 0 structure geometric fit, and the compatibility between soft-and hardsegments. For polyurethanes with same polyester soft segmental molecular weights, with other things being t To whom correspondence should be addressed.equal, the soft-and hard-segmental compatibility increases with increasing polyester -...

The influence of diol chain extender on morphology and properties of thermally-triggered UV-stable self-healing polyurethane coatings

“…Selim et al and Gomez et al reported that symmetric and linear diisocyanates, such as hexamethylene diisocyanate (HDI), promote crystallinity and phase-separation via long-range ordering of hydrogen bonds, while asymmetrical and bulky isophorone diisocyanate (IPDI) promotes phase-mixing [24,25]. In other studies it was observed that CE with even number of carbon atoms, with the exception of ethylene glycol, promote crystallinity and packing [26][27][28].…”

Utjecaj vrste i udjela diizocijanata na toplinska i mehanička svojstva mješavina poliuretana i polikarbonata

“…Na DSC krivulji elastomera PU s manjim udjelom diizocijanata (PU ES MDI 2/1) vidljiva je pojava staklišta (T g ) na −27,1 °C, a na višim temperaturama vidljiva je pojava ši-rokog endotermnog prijelaza na 119,6 °C koji odgovara talištu tvrdog segmenta. 12,13 Stupanj kristalnosti elastomera PU (χ c ) izračunat je na osnovi vrijednosti ΔH m dobivenih iz mjerenja DSC preko izraza (1):…”

Transparent thermoplastic polyurethanes based on aliphatic diisocyanates and polycarbonate diol

“…Two principal vibrational regions have been specially studied, the N-H stretching vibration (3200-3500 cm À1 ) and the carbonyl absorption region (1630-1730 cm À1 ; Figure 4). 31,[35][36][37][38] The carbonyl absorption region is of particular interest since it gives information about inter urethane hydrogen bonding. Frequency shifts to lower values occur due to hydrogen bonding.…”

“…29,31,[35][36][37][38] A peak around 3320 cm À1 is related with hydrogen-bonded N-H groups, while the free N-H appears at higher wavelength. 10,21,26,31,34 A band around 3320 cm À1 that increases in sharpness and intensity as the HDI prepolymer content increases is observed (Figure 4(a)). As in the other techniques, a big change is noticed when changing from HDI-50 to HDI-70, indicative of increasing N-H hydrogen bonding, manifested by a more ordered hard segment structure as can be observed in the areas relation between N-H and methylene groups in Table 2.…”