New thermoplastic poly(carbonate-urethane)s based on chain extenders with sulfur atoms

New thermoplastic segmented polyurethanes were obtained by a one-step melt polyaddition using 40, 50 and 60 mol% poly(hexane-1,6-diyl carbonate) diol of \(\bar{M}_{n} = 860\) g mol^?1, 1,1′-methanediylbis(4-isocyanatobenzene) and 2,2′-[sulfanediylbis(benzene-1,4-diyloxy)]diethanol, 2,2′-[oxybis(benzene-1,4-diylsulfanediyl)]diethanol or 2,2′-[sulfanediylbis(benzene-1,4-diylsulfanediyl)]diethanol as a chain extender. FTIR, atomic force microscopy, differential scanning calorimetry and thermogravimetry were used to examine the polyurethanes’ structure and thermal properties. Moreover, their Shore A/D hardness, tensile, adhesive and optical attributes were determined. They were transparent high-molar-mass materials showing good tensile strength (up to 51.9 MPa). The polyurethanes exhibited improved adhesion to copper taking into consideration that of conventional ones, and middle or high refractive index values (1.57–1.60), and both these parameters increased with an increase of the content of sulfur atoms in the polyurethane chain. The newly obtained polyurethanes can be considered as materials for numerous medical and optical appliances.     

Porous DMN-co-GMA copolymers modified with 1-(2-hydroxyethyl)-2-pyrrolidone

Journal of Thermal Analysis and Calorimetry - Porous microspheres obtained from 2,3-epoxypropyl methacrylate (GMA) and 1,4-di(methacryloyloxymethyl) naphthalene (DMN) were modified by the reaction...     

New thermoplastic poly(thiourethane-urethane) elastomers based on hexane-1,6-diyl diisocyanate (HDI)

Two series of new thermoplastic poly(thiourethane-urethane) elastomers (EPTURs), with different hard-segment content (40–60 wt%), were synthesized by a one-step melt polymerization from poly(oxytetramethylene) diol (PTMO) of $ \overline{M}_{\text{n}} $  = 1,000 g mol^?1 or poly(hexamethylene carbonate) diol (PHCD) of $ \overline{M}_{\text{n}} $  = 860 g mol^?1 as a soft segment, hexane-1,6-diyl diisocyanate and (methylenedi-1,4-phenylene)dimethanethiol as a chain extender at the NCO/(OH + SH) molar ratio of 1. The structures of all the EPTURs were examined by Fourier transform infrared spectroscopy (FTIR), atomic force microscopy and X-ray diffraction analysis. Their thermal behavior was investigated by means of differential scanning calorimetry and thermogravimetric analysis (TG). For the chosen polymers the gaseous products evolved during the decomposition process were analyzed by TG-FTIR. Moreover, physicochemical, adhesive and tensile properties as well as Shore A/D hardness were determined. The resulting high-molecular-mass EPTURs were stable up to 254–262 °C, as measured by the temperature of 1 % mass loss. They decomposed in three or four stages. The main decomposition products were carbonyl sulfide, isocyanate, carbon dioxide, aromatic hydrocarbons as well as aliphatic ethers and aldehydes (in PTMO series) and alcohols (in PHCD series). All the polymers showed partially crystalline structures, associated with crystallization of thiourethane hard segments. Their melting temperatures were in the range of 184–186 °C. The PTMO series EPTURs exhibited better low-temperature properties (glass-transition temperature in the range of ?64 to ?44 vs. ?26 to ?22 °C), but poorer tensile strengths (20–28 vs. 37–43 MPa). These EPTURs showed improved adhesive properties in comparison with their polyurethane analogs.     

The synthesis and characterization of new thermoplastic poly(carbonate-urethane) elastomers derived from HDI and aliphatic–aromatic chain extenders

New thermoplastic poly(carbonate-urethane) elastomers (TPCUs) were prepared by a one-step melt polymerization from 20–80 mol% poly(hexane-1,6-diyl carbonate) diol of as a soft segment, hexane-1,6-diyl diisocyanate and 2,2′-[methylenebis(1,4-phenylenemethylenethio)]diethanol, 3,3′-[methylenebis(1,4-phenylenemethylenethio)]-dipropan-1-ol or 6,6′-[methylenebis(1,4-phenylenemethylenethio)]dihexan-1-ol (H) as new chain extenders at the NCO/OH molar ratio of 1 in the presence of dibutyltin dilaurate as a catalyst. The structures of the TPCUs were examined by FTIR spectroscopy, X-ray diffraction analysis, scanning electron microscopy and atomic force microscopy (AFM). The TPCUs were also characterized by physicochemical, thermal (by differential scanning calorimetry (DSC) and thermogravimetry) and tensile properties as well as Shore A/D hardness. The resulting TPCUs were colorless polymers, showing ordered structures including semicrystalline, with the highest ability to crystallize exhibited by the polymers derived from diol H. The polymers with the soft-segment content of 40–80 mol% (56.4–25.7 wt% of hard segments) exhibited a microphase separation shown by DSC and AFM. The TPCUs showed tensile strength in the range of 8.8–23.3 MPa and elongation at break in the range of 240–670%.     

Studies of thermal properties of di(methacryloyloxymethyl)naphthalene–divinylbenzene (DMN–DVB) copolymer and its alkyl-bonded derivatives

This paper presents the thermal properties of highly crosslinked di(methacryloyloxymethyl)naphthalene–divinylbenzene (DMN–DVB) copolymeric microspheres containing polar groups in the structure and their alkyl-bonded derivatives. C₈ and C₁₈ alkyl chains were introduced into the aromatic rings of the DMN–DVB porous copolymer by means of the Friedel–Crafts reaction. As a source of C₈ and C₁₈ alkyl chains, octyl and octadecyl chlorides were used. It was necessary to check whether the introduction of alkyl chains into the structure of polymeric packing had an impact on its thermal properties. The studies were carried out by thermogravimetry coupled online with FTIR spectroscopy and differential scanning calorimetry in inert atmosphere (helium). It was stated that the modified materials showed 20 and 50% mass losses at higher temperatures than the non-modified one while 1% mass loss was observed at lower temperatures. Moreover, an analysis of volatile decomposition products was performed.

     

New thermoplastic poly(carbonate-urethane)s based on diphenylethane derivative chain extender

Journal of Thermal Analysis and Calorimetry - Two series of new sulfur-containing thermoplastic poly(carbonate-urethane)s (PCURs) were prepared by a one-step melt polyaddition from diphenylethane...     

The synthesis and characterization of new thermoplastic poly(thiourethane‐urethane)s

New thermoplastic segmented poly(thiourethane‐urethane)s (SPTUUs) were prepared by a one‐step melt polymerization from 20 to 80 mol % poly(tetramethylene oxide) of = 1000 or poly(hexamethylene carbonate) diol (PHCD) of = 860 as soft segments, hexamethylene diisocyanate (HDI) and bis[4‐(mercaptomethyl)phenyl]methanone (BMMPM) as a new dithiol chain extender at the NCO/(OH + SH) molar ratio of 1 in the presence of dibutyltin dilaurate as a catalyst. The structures of the SPTUUs were examined by FTIR, X‐ray diffraction analysis, and scanning electron microscopy. The SPTUUs were also characterized by physicochemical, thermal, and tensile properties as well as Shore A/D hardness. The SPTUUs with the PHCD soft segments showed better tensile properties than those with the PTMO soft segments. A nonsegmented polythiourethane based on BMMPM and HDI is also described. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1770–1782, 2008