Polymer International 43 (1997) 217 222

Cast Polyurethanes Based on Castor Oil and Fluorescein

S. Ramesh, G. N. Mahesh, K. A. Subramanian & Ganga Radhakrishnan*
Polymer Division, Central Leather Research Institute, Adyar, Madras 600 020, India (Received 10 January 1996 ; revised version received 1 October 1996 ; accepted 4 November 1996)

Abstract : Cast polyurethanes based on castor oil, uorescein and tolylene diisocyanate have been synthesized. The polyurethanes were characterized by Fourier transform infrared spectroscopy. The thermal stabilities of the polymers were determined using a thermogravimetric analyser. From the dierential scanning calorimetric analysis, change in the glass transition temperature of the soft segment was observed as the molar ratio and feed composition of the uorescein were varied. Polym. Int. 43, 217 222 (1997) No. of Figures : 4. No. of Tables : 1. No. of Refs : 28

Key words : polyurethane, castor oil, uorescein, FTIR, thermal stability.

INTRODUCTION The introduction of coloured moieties into polymer chains has gained prominence recently owing to their inherent non-leaching behaviour and good light fastness combined with the special properties of polymers.1h3 Their impact is now felt in various specialty elds such as liquid crystalline displays,4 ink-jet printing5 and UVcurable coatings.6,7 Another important area where these polymeric colourants have made a signicant contribution is in the development of colour toners for electrophotography.8,9 The fascinating range of colours available to the synthetic chemist for manipulating colour toners to a users requirements has led to the present dramatic increase in their use. Fluorescein and its derivatives have been used in various novel applications : for example, as colour formers in colour imaging,10 coloured adhesives11 and iridescent decorative boards,12 as dyes in electro-optic polymers,13 and as anti-reection layers on image
* To whom all correspondence should be addressed.

screens,14 holograms,15 non-linear optical16 and recording materials.17,18 In electrophotography they are used as sensitizers and colour toners. Previously, uorescein has been used as a unit to prepare polyesters19 and metal-containing polydyes and as the terminal unit in polyethers.20 Polyurethanes are versatile polymers with wideranging applications. With numerous combinations possible in their synthesis, they yield materials that range from highly viscous liquids to exible or rigid elastomers. The use of renewable resources has received widespread attention in recent times because of the global interest in environmentally friendly techniques. Castor oil is one such substance, which has been used as a polyol for the preparation of polyurethane-based coatings,21 ionomers,22 adhesives and interpenetrating polymer networks.23 h25 There has also been a patent report on the use of uorescein dyes, castor oil and soya bean oil-based polymers for use in electrophotography.26 In an earlier paper we described the use of uorescein to prepare segmented polyurethanes.27 In 217

( 1997 SCI. Polymer International 0959-8103/97/$17.50

Printed in Great Britain

218 this paper we report our investigation on cast polyurethanes based on castor oil and uorescein. EXPERIMENTAL

S. Ramesh et al. 1 h and cast over a silicon rubber trough to form lms with a thickness in the range 01 015 cm. This synthesis of cast polyurethanes is shown in Scheme 1. The composition and codes of the polyurethanes are given in Table 1. In two of the compositions, uorescein was thoroughly mixed with the polyol in the presence of solvent before the addition of TDI. The isocyanate content in all the reactions was kept in an excess of 01 mol for the formation of cast lms. The lms were then dried at 60C in vacuum to remove traces of solvent molecules before characterization. All the compositions yielded bright red coloured lms.

Materials
Castor oil obtained from a commercial source was dried in vacuum at 105C for 5 h before use (OH No. 164). Tolylene diisocyanate (TDI) (a mixture of 80% 2,4 and 20% 2,6 isomers) and dibutyltin dilaurate (DBTDL) (Aldrich) were used as received. Fluorescein (S.D. Fine Chem., India) was reuxed with HCl solution, ltered and recrystallized from acetonealcohol mixture before use. The solvents methyl ethyl ketone (MEK) and dimethylformamide (DMF) were distilled and stored over molecular sieves (type 4A) until use.

Measurements
Fourier transform infrared (FTIR) spectra of the polymers were recorded on thin lms using a Nicolet Impact 400 spectrometer. To prepare thin lms for FTIR studies, a small amount of the sample was precipitated in methanol, dissolved in DMF, cast over a pool of mercury and the solvent evaporated at 60C in air. Thermogravimetric analysis was carried out using a Du Pont 951 instrument at a heating rate of 20C min~1 in nitrogen. Dierential scanning calorimetry (DSC) was carried out on a Du Pont 910 instrument equipped with a standard cell at a heating rate of 10C min~1 under nitrogen. Samples were not aged prior to testing in order to prevent the disappearance of short-range ordering phenomena, if any. Dierent samples of the same material were scanned for reproducibility. Low temperature DSC analysis was carried out by quenching

Preparation of cast polyurethanes

Cast polyurethanes were prepared by either a one-stage (diol blend) or two-stage (prepolymer) route. Castor oil (10 g) was placed in a three-necked ask and appropriate molar ratios of TDI were added with rapid stirring under nitrogen. The temperature of the reaction was kept at 60C. After an hour, the temperature of the reaction mixture was raised to 90C and kept for a further 2 h. The reaction temperature was then lowered to 60C, after which uorescein (dissolved in 60% DMF and 40% MEK) was added, followed by 001 g of the catalyst, DBTDL. The reaction mixture was stirred for

Scheme 1 POLYMER INTERNATIONAL VOL. 43, NO. 3, 1997

Cast polyurethanes
TABLE 1. Compositions and properties of the polymers Polymer compositions Codes Hard segment content (%) 4007 4007 5420 5420

219

T (C) g

Tensile strength at break (MPa)

Elongation at break (%)

Castor Castor Castor Castor

oil/2TDI/Fluorescein oil Fluorescein/2TDI oil/3TDI/2Fluorescein oil 2Fluorescein/3TDI

CTF1 CTF2 CTF3 CTF4

170 70 75 220

218 weak brittle brittle

172 weak brittle brittle

the samples in the cell using liquid nitrogen. The amount of sample taken for each run was 5 ^ 02 mg. Mechanical properties of the polymers were evaluated using an Instron Universal Testing Machine model 1112 at a crosshead speed of 125 cm min~1. The lms, with a thickness in the range of 01 015 cm, were cut into dumb-bell shapes of length 17 cm and breadth 11 cm and were tested at 25C. Five specimens were subjected to testing to obtain an average value.

RESULTS AND DISCUSSIONS

FTIR analysis
The FTIR spectrum of the polyurethane CTF1 is given in Fig. 1. The urethane wNH stretching is observed at

3335 cm~1. The reduction in the band width here, when compared with polyether systems, is due to the absence of hydrogen bond interacting sites in the mainly hydrocarbon backbone of the castor oil units. As the castor oil backbone is mainly made up of aliphatic methylene units, an intense absorption at 2973 cm~1 is seen. The bonds for the carbonyl of the ester group in the ricinoleic acid of the castor oil unit and the carbonyl of the urethane groups are merged and are seen as a broad signal at 1736 cm~1. The CxC stretching of the unsaturated group of the castor oil and that of the aromatic units of the TDI and uorescein are observed at 1607 cm~1. A band due to CwN stretching and NwH deformation (amide II) is observed at 1541 cm~1. The four polyurethanes in this study were all prepared from the same components, diering only in composition and method of preparation (single stage one-step process, or

Fig. 1. FTIR spectrum of CTF1. POLYMER INTERNATIONAL VOL. 43, NO. 3, 1997

220 a two-stage prepolymer process). Therefore the spectra of the polyurethanes were similar, with variations only in the intensities of certain peaks (CxC aromatic, CxO stretching etc.).

S. Ramesh et al. Hence CTF2 yields about 20% residual weight, whereas the other systems yield about 25%.

DSC studies
The DSC data for the polyurethanes are given in Fig. 3 and Table 1. The glass transition temperatures of the polyurethanes were taken as the midpoint of the transition. Comparing CTF1 and CTF3, as the amount of hard segments (isocyanate and chain extender) increases, the glass transition temperature (T ) of the g soft segments shifts towards higher values. This is because the increased quantity of hard segments embedded in the soft segments acts as a hindrance to efficient phase separation. Comparing polymers of the same components, but with dierent feed compositions (CTF1 and CTF2), we observe again that the T shifts towards higher values. g The increased T of CTF2 in comparison with CTF1 is g due to interphase mixing of the soft and the hard segments. The hard segments are well dispersed in the soft segments, resulting in the higher T of CTF2. The uog rescein is well dispersed in the polyol matrix before the start of the reaction, hence the hard segments formed are also well dispersed in the soft segments, which hinders their ordered arrangement, leading to an

Thermogravimetric analysis
Figure 2 shows the thermograms of the polyurethanes. A multistage decomposition pattern is observed since the polyurethane is made up of dierent chemical units. No major change in the decomposition pattern was observed for the polyurethanes studied, since after the inherent cleavage of the urethane units around 230C, the polymers start decomposing. The apparent high thermal stability is due to the non-isothermal experimental conditions and non-volatile nature of the decomposition products. In the case of CTF3, the number of urethane linkages between the isocyanate of TDI and the hydroxy groups of uorescein is greater. Since the urethane linkage is the least stable, CTF3 starts losing weight at 150C. In the case of CTF4, which is similar in composition to CTF3, the number of urethane linkages is signicantly less, since the polyol and uorescein are mixed prior to reacting with TDI. The polyurethane backbone formed from castor oil and TDI is more stable than that from uorescein and TDI.

Fig. 2. Thermogravimetric curves of polyurethanes : ( ) CTF1, ( ) CTF2, ( ) CTF3 () CTF4. POLYMER INTERNATIONAL VOL. 43, NO. 3, 1997

Cast polyurethanes

221

Fig. 3. DSC curves of polyurethanes.

increase in T . On comparing CTF2 and CTF4, the g introduction of more hard segments in the latter leads to aggregation. The increased purity of the polyol segment decreases the T of the soft segment. This may g be due to phase inversion. All the curves are reproducible. The case of CTF3 and CTF4 should be similar. However, the reverse phenomenon was observed here, where the soft segments of CTF4 have a lower T . Here g also the uorescein was well mixed with the polyol before the start of the reaction. The overall molar ratio of the uorescein units plays a crucial role since the total content of uorescein is twice that of the polyol. So the quantity of hard segment units formed exclusively of TDI and uorescein will be very high, leading to enormous dierences in polarity between the two segments. Under these conditions the hard segments tend to aggregate. The T at [22C is real and reprog ducible. In the case of CTF4, because of the large amount of hard segment formation, aggregation of the hard segments takes place, leading to purity of the soft segments, which results in a decrease of T . This is subg stantiated by the fact that, apart from the low soft segment T , a clear transition at ]21C is observed, g which could be due to a mixed phase transition.

centage elongation at break show that sample CTF1 is an elastomer having better properties than all the other combinations studied. One reason for this is that the step reaction polymerization to yield stoichiometrically identical end-capped prepolymer, followed by chain extension, leads to polymers of appreciable molecular weight and narrow distribution.28 This combination also has the optimum content of hard and soft segments, so that the polymer as a whole is elastic. With the same components, the composition CTF2 was weak. In the cases of CTF3 and CTF4, even though both T g values were below room temperature, the samples were brittle. The reason for this observed brittleness is the higher ratio of isocyanate, which undergoes marginal branching/crosslinking side-reactions. CONCLUSIONS Inherently coloured polyurethanes were prepared using castor oil and uorescein by either a one-step process or a prepolymer process. The glass transition temperatures of the polyurethanes could be altered by using dierent feed compositions. The elastomeric product obtained was of moderate strength and had good elongation. ACKNOWLEDGEMENTS The Council of Scientic Industrial Research (CSIR), India, is acknowledged by S. Ramesh, for his Research

Mechanical properties
The mechanical properties of the polyurethanes are given in Table 1. The values of tensile strength and perPOLYMER INTERNATIONAL VOL. 43, NO. 3, 1997

222 Associateship, and by G. N. Mahesh for his Research Fellowship.

S. Ramesh et al.
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POLYMER INTERNATIONAL VOL. 43, NO. 3, 1997