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Poly(Urethane-Urea)S Based on Oligocarbonatediols Comprising Bis(Carbamate)Alkanes

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Poly(Urethane-Urea)S Based on Oligocarbonatediols Comprising Bis(Carbamate)Alkanes Polymer Journal, Vol. 37, No. 10, pp. 742–753 (2005) Poly(urethane-urea)s Based on Oligocarbonatediols Comprising Bis(carbamate)alkanes Piotr PAWŁOWSKI,1 Adam SZYMAN´ SKI,1 Janusz KOZAKIEWICZ,2 y Jarosław PRZYBYLSKI,2 and Gabriel ROKICKI1; 1Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw, Poland 2Industrial Chemistry Research Institute, Rydygiera 8, 01-793 Warsaw, Poland (Received April 6, 2005; Accepted June 20, 2005; Published October 15, 2005) ABSTRACT: In this work the results of studies on the prepolymeric method of obtaining poly(urethane-urea)s from oligocarbonatediols and isophoronediisocyanate (IPDI), cured with water vapor, are presented. ,!-Bis(2- hydroxyethoxycarbonylamino)alkanes (dihydroxydiurethanes, DHDU) incorporated into the structure of oligocarbon- atediols and as pseudo-chain extenders were used for the synthesis of prepolymers. The oligocarbonatediols were obtained by the thermal polymerization of trimethylene carbonate (TMC) using 1,3-propanediol and DHDU as initia- tors. The poly(urethane-urea)s obtained exhibited very good mechanical properties (e.g.: tensile strength of 45.5 MPa and elongation at break up to 580%). [DOI 10.1295/polymj.37.742] KEY WORDS Poly(urethane-urea)s / Oligocarbonatediols / Isophoronediisocyanate / Trimethy- lene Carbonate / Dihydroxydiurethanes / Polyurethanes based on oligocarbonatediols are In the case of anionic polymerization of cyclic known since 1990s. They are characterized by oxida- six-membered carbonates decarboxylation does not tive and hydrolytic stability, and therefore they can be occur; however, in the post-reaction mixture some used to obtain materials for biomedical applications.1,2 amount of the unreacted monomer can be present. Polycarbonate fragments indicate a relatively high The process is most often initiated by potassium, hydrolytic stability. The hydrolysis of oligocarbonates sodium and lithium alkoxides.9 Amine initiators, most leads to the formation of hydroxyl groups and CO2, often hypernucleophilic derivatives of pyridine or i.e. products which do not catalyze further hydrolysis. other cyclic amines, e.g. 4-N,N-dimethylaminopyri- Soft segments of polyurethanes in the form of ali- dine (DMAP) and 1,8-diazabicyclo[5,4,0]undec-7-ene phatic carbonate oligomers are usually obtained by (DBU) are also used as catalysts of the anionic poly- the condensation method from 1,6-hexanediol and merization.10 phosgene or carbonate acid esters.3,4 The coordination polymerization of six-membered Oligocarbonatediols for polyurethanes can also be carbonates is carried out in the presence of organome- obtained by copolymerization of oxiranes with carbon tallic catalysts containing Zn, Sn, Al atoms; tin(II) dioxide in the presence of organozinc catalysts.5 In or- octoate is most often used.11 Admittedly, the polymer- der to decrease the molecular weight of such aliphatic ization is not accompanied by decarboxylation and no polycarbonates, high-molecular weight poly(propyl- ether groups are formed, but part of the polymer ene carbonate)s were subjected to transesterification chains have a terminal OH group protected by the acid reaction with 1,4-butanediol or 1,6-hexanediol.6,7 radical of the catalyst.12 The formation of a fraction of the oligomers terminat- Some cyclic six-membered carbonates, like tri- ed with less reactive secondary OH groups was a dis- methylene carbonate (TMC), undergo spontaneous advantage of this method. The removal of the remain- thermal polymerization.13 Kricheldorf suggests that ing polymerization and transesterification catalysts at elevated temperature a zwitterion is formed, of from the product caused an additional difficulty. which the alkoxide anion initiates the chain growth Six-membered cyclic carbonates homopolymerize, according to the anionic mechanism (Scheme 1). contrary to five-membered carbonates. During the The formation of ether groups during the enzymatic polymerization of six-membered cyclic carbonates polymerization of cyclic carbonates carried out in the proceeding according to the cationic mechanism, presence of lipase enzyme Canadida Antartica was decarboxylation takes place, and ether bonds are not observed.14 The yield and molecular weight of formed. The presence of ether bonds in the structure the polycarbonate obtained with an enzymatic catalyst of soft polyurethane segments decreases the oxidation very strongly depend on the reaction conditions. resistance of polyurethane.8 Taking the above into consideration, we used the yTo whom correspondence should be addressed (Tel: +48-22-660-7562, FAX: +48-22-628-2741, E-mail: [email protected]). 742 Poly(urethane-urea)s Based on Oligocarbonatediols O O _ O O + O O O O + O O O O Scheme 1. thermal method of polymerization to obtain oligo(tri- sample the spectrum was recorded based on 200 methylene carbonate)s which can be applied in the impulses. The samples were prepared by dissolution oxidative resistant polyurethane synthesis. The result- of the studied polymer in THF and mixing it with a ant oligomers are terminated on both sides with solution of 2,5-dihydroxybenzoic acid used as a hydroxyl groups and do not contain ether groups in MALDI-TOF matrix. DSC studies were performed their structure. The non-necessity of using catalysts in the temperature range from À120 Ctoþ60 C is an additional advantage of this method. using a Perkin Elmer Pyris 1 calorimeter at a heating Little information can be found in the literature on rate of 20 C/min for samples of 10–25 mg mass. the application of oligo(trimethylene carbonate)s in the synthesis of polyurethanes. Macrodiols obtained Synthesis of Trimethylene Carbonate (TMC)16 from TMC were applied for the preparation of poly- In a 500 cm3 round-bottomed flask 110 g (1.45 mol) urethanes using 4,40-diphenylmethane diisocyanate of 1,3-propanediol, 156 g (1.73 mol) of dimethyl car- (MDI).15 Polyurethanes were obtained in a one-step bonate and 3.68 g (0.02 mol) of zinc acetate were process using 1,4-butanediol and 1,3-propanediol as placed. In the first stage the reaction was carried out chain extenders. under a reflux condenser for 30 min. In the second In this work we present the results of studies on the stage the methanol formed was distilled off. The poly- application of oligo(trimethylene carbonate) diols to condensation progress was monitored by collecting obtain poly(urethane-urea)s using water vapor as a samples of the reaction mixture and observing curing agent. The effect of the presence of ,!-bis- changes in the absorption band derived from hydroxyl (2-hydroxyethoxycarbonylamino)alkanes (DHDU) in groups by means of infrared spectroscopy and observ- the oligocarbonate diols on the poly(urethane-urea)s ing the amount of methanol formed. Then, the excess mechanical properties is also presented. The poly- of dimethyl carbonate was distilled off and the reac- (urethane-urea)s obtained may find application in the tion was carried out under reduced pressure (2 mmHg) production of biocompatible medical materials. at 133–135 C for 4 h. After this time the temperature of the bath was increased to 240 C and the depoly- EXPERIMENTAL merization process was carried out with distilling off the product. The crude product obtained (120.1 g, Materials 81% yield) was then crystallized from THF. 108 g Ethylene carbonate, dimethyl carbonate, 1,3-pro- (73% yield) of white crystals of m.p. 46–47 C were panediol, 4-N,N-dimethylaminopyridine, 1,2-diamino- obtained. 1 ethane, 1,6-diaminohexane, isophoronodiisocyanate H NMR 400 MHz (CDCl3) (ppm) = 2.11 (m, (IPDI) (Aldrich), Chirazyme L-2 enzyme (Roche), OC(O)OCH2CH2), 4.42 (t, OC(O)OCH2CH2, J ¼ zinc acetate, methylene chloride, THF (POCh Gliwice, 5:6 Hz). Poland) were used without additional purification. Synthesis of Oligocarbonatediol from Trimethylene Measurement Methods Carbonate and 1,3-Propanediol 1H NMR and 13C NMR spectra were recorded by Polymerization Thermally Initiated. In a 150 cm3 means of a Varian VXR 400 MHz spectrometer. Deu- round-bottomed flask equipped with a mechanical terated solvents were used and tetramethylsilane stirrer and thermometer 52 g (0.51 mol) of trimethyl- served as internal standard. IR spectra were measured ene carbonate and 2.72 g (0.036 mol) of 1,3-propane- using a Biorad FT IR spectrophotometer. Samples for diol were placed. The reaction system was heated in analysis were prepared in the form of pellets with a nitrogen atmosphere for 24 h. The reaction progress KBr. The chemical structure of oligocarbonatediols was monitored using IR spectrophotometry observing was studied by means of a MALDI-TOF mass spec- the absorption band at 760 cmÀ1 characteristic for the trometer (Kratos Kompact MALDI 4 V5.2.1 using cyclic carbonate skeleton vibrations. 62.6 g of liquid, 2,5-dihydroxybenzoic acid as the matrix). The appara- colorless oligo(trimethylene carbonate) of Mn ¼ tus was equipped with a nitrogen laser of 337 nm 1500 Da was obtained. 1 wavelength and length impulses of 3 ns. For each H NMR 400 MHz (DMSO-d6) (ppm) = 1.30 (m, Polym. J., Vol. 37, No. 10, 2005 743 P. PAWŁOWSKI et al. 1 OCH2CH2); 3.51 (m, 4H, HOCH2), 4.10 (m, OCH2- H NMR 400 MHz (DMSO-d6): (ppm) = 2.92 (s, CH2). 4H, NHCH2); 3.50 (t, 4H, CH2O, J ¼ 4:8 Hz); 3.92 FT IR (KBr): 3365, 2960, 1747, 1470, 1245, 1034, (t, 4H, HOCH2CH2, J ¼ 4:8 Hz); 4,71 (s, 2H, À1 933, 791 cm . HOCH2); 6.73 and 7.09 (m, 2H, OC(O)NH). Elemental analysis: C 46.77, H 6.54. FTIR (KBr): 1687, 1537, 1467, 1455, 1271, 1105. Polymerization Initiated in a Microwave Oven. C8H16N2O6 (236.23 g/mol): Calcd: C 40.68, H 6.83, 15 g (0.15 mol) of trimethylene carbonate and 0.8 g N 11.86; Found: C 40.12, H 6.89, N 11.19. (0.01 mol) of 1,3-propanediol were placed in a glass ampoule.
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