Reactive & Functional Polymers 50 (2002) 217223 www.elsevier.

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A facile and efcient method for preparation of chiral supported poly(styrenedivinylbenzene) copolymers
Ali-Reza Mahdavian*, Sepideh Khoee
Iran Polymer Institute, P.O. Box 14965 /115, Tehran, Iran Received 19 December 2000; received in revised form 28 June 2001; accepted 30 June 2001

Abstract A new and efcient method for preparation of optically active poly(styrenedivinylbenzene) copolymers (PS-DVB) is presented here. This is carried out by FriedelCrafts acylation reaction of chiral N -phthaloyl L-leucine acid chloride with PS-DVB beads in the presence of aluminum chloride as Lewis acid catalyst and 1,2-dichloroethane as the solvent at ambient temperature. Reagents amounts and reaction conditions are mentioned and four samples with different amounts of functionality have been prepared. Final products were characterized by FT-IR and elemental analysis. The results obtained conrm that the above modication in preparation of chiral supported PS-DVB has been achieved well and in moderate yield. 2002 Elsevier Science B.V. All rights reserved.
Keywords: Poly(styrenedivinylbenzene) copolymer; N -Phthaloyl acylation; Functional polymers
L-leucine

acid chloride; Chiral supported polymers; FriedelCrafts

1. Introduction During the last few decades, special attention have been paid to synthesis of partially functionalized polystyrene [13]. This is due to the low cost and wide applicability of this polymer. Chemical modication of resins based on polystyrene has been studied increasingly, because the aromatic ring of styrene group could easily

* Corresponding author. Tel.: 1 98-21-602-6317; fax: 1 98-21602-6500. E-mail address: a.mahdavian@proxy.ipi.ac.ir (A.-R. Mahdavian).

perform electrophilic aromatic substitution reactions such as nitration and sulfonation [46]. FriedelCrafts acylation on polystyrene is another attractive subject that has been used for different systems, such as preparation of reagents [710], ion-exchange resins [1113] and also development of thermal properties homopolymers and copolymers of polystyrene [14 16]. The past 30 years have experienced an exponential growth in the rational design of methods for stereoisomer separation. The rst chiral stationary phases used for separation of enantiomers were naturally occurring polymers such as cellulose and starch [17]. However, the use of synthetic chiral polymers for these kinds

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of separations could be divided into two categories: (i) synthetic polymers such as chiral stationary phase and (ii) polymer supported chiral stationary phase. The supported polymers with chiral groups are based on inorganic polymers such as silica [1820] or organic polymers such as polystyrene [2124]. Previously we had used N -phthaloyl L-leucine acid chloride to prepare novel optically active polymers via cycloaddition polymerization [25]. In this study, we carried out FriedelCrafts acylation reaction of the above-mentioned acid chloride with poly(styrenedivinylbenzene) copolymer to produce chiral stationary phase which could be used as packing in column chromatography. To our knowledge, this is the rst report of preparation of chiral polymers via FriedelCrafts acylation in a direct reaction. 2. Experimental

2.3. Suspension polymerization of styrenedivinyl benzene

The water bath temperature was 708C and the reaction vessel equipped with thermometer, nitrogen gas inlet, etc. were placed in it; 9.2 3 10 2 3 g Tween 80 (surfactant), 1.0 g poly vinylpyrolidone (PVP) as stabilizer and 500 ml demineralized water were added to the reactor and stirred until dissolution was complete. Then the above solution was diluted to 1620 ml. After the solution temperature reached 708C (isothermal conditions), the reactor was purged with nitrogen gas; 9.6 g divinyl benzene, 120 g styrene (8% by weight) and 1.2 g benzoyl peroxide were premixed and added to the reactor. The reaction mixture was mechanically stirred for 5 h. Then it was ltered off, washed with distilled water and dried. The beads obtained were sieved to separate the 200400 mesh portion. This part was suspended in 10% aqueous solution of HCl (v / v) and stirred for 1 h at 508C. Then it was ltered, washed with distilled water and dried at 808C for 12 h.

2.1. Materials
Reagents were purchased from Merck and Fluka. Styrene monomer was received from Tabriz Petrochemical Inc., Iran. Styrene and divinyl benzene were washed with 5% solution NaOH / water (w / v) and distilled water, respectively to remove inhibitors and then stored at 08C before use. All other reagents were used without purication.

2.4. Preparation of N-phthaloyl L-leucine acid chloride ( 4 )

N -Phthaloyl L-leucine acid chloride ( 4 ) was prepared through two steps (Scheme 1). First, from the condensation reaction of phthalic anhydride ( 1 ) and L-leucine ( 2 ) (total yield of

2.2. Equipment
Suspension polymerization was performed using a glass reactor, steel water bath, controllable speed motor equipped with three curved blades and at-type steel bafe. Infrared spectra were recorded on a BrukerIFS 48 FT-IR spectrophotometer. Spectra of solids were obtained using KBr pellets. Vibrational transition frequencies are reported in wavenumber (cm 2 1 ). Elemental analyses were run by a CHN-O-RAPID Heraeus, GMBH instrument.

Scheme 1.

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98%) and second, the reaction of the corresponding product ( 3 ) with thionyl chloride, which resulted in a deep yellow viscous liquid 25 with 100% yield ([a] D 5 2 6.678 (0.060 g in 10 ml CHCl 3 )) [26].

3. Results and discussion Beads of poly(styrenedivinylbenzene) copolymer (PS-DVB) from 200400 mesh were used in this work. The PS-DVB copolymer prepared by suspension polymerization contains a small amount of adsorbed poly vinylpyrolidone (PVP) as stabilizer. On the other hand, functionality of PS-DVB beads is determined qualitatively and quantitatively by elemental analysis and measurement of nitrogen percent. So the nitrogen atoms exist in the chemical structure of adsorbed PVP, leading us to incorrect estimation of the chemical modication of PS-DVB via FriedelCrafts acylation. In order to remove the adsorbed PVP, PS-DVB powder was poured into 10% aqueous solution of HCl (v / v) and stirred for 1 h at 508C. Therefore the PVP on the surface of beads are dissolved in aqueous phase. The above mixture was ltered off and washed with plenty of water until the ltrate was neutralized. The powders were dried in an oven for 12 h at 808C and analyzed by elemental analysis. As shown in Table 2, there is no trace of nitrogen relating to the adsorbed PVP. N -Phthaloyl L-leucine acid chloride ( 4 ) was prepared according to the steps shown in Scheme 1. N -Phthaloyl L-leucine ( 3 ) is synthesized from the condensation reaction of Lleucine ( 2 ) as a chiral amino acid and phthalic anhydride ( 1 ) in the presence of triethylamine. After further purication, the carboxylic acid ( 3 ) was converted to the corresponding acid chloride ( 4 ) in the presence of thionyl chloride.

2.5. Friedel Crafts acylation of N-phthaloyl L-leucine acid chloride ( 4 ) with PS-DVB (typical procedure)
A 0.25-g aliquot (8.94 3 10 2 4 mol) of chiral acid chloride ( 4 ) was dissolved in 8 ml 1,2dichloroethane at room temperature in a 25-ml round-bottomed ask. The temperature of the above solution was cooled to 08C in an ice bath; 0.51 g PS-DVB powder was gradually added to the above acid chloride solution while stirring magnetically at 08C. At the end of addition, it was allowed to stir for 30 min at this temperature and then 0.48 g (3.58 3 10 2 3 mol) AlCl 3 was added portion-wise to this mixture. After 60 min stirring at 08C, the temperature of the reaction mixture was raised to room temperature. The reaction was carried out for 2 h and then it was ltered off. Washing of the obtained product was performed according to the following procedure: (i) 10% aqueous solution of HCl (v / v) (5 3 20 ml); (ii) 10% aqueous solution of NaOH (w / v) (5 3 20 ml); (iii) Distilled water (5 3 20 ml); (iv) Ethanol (5 3 10 ml); (v) THF (5 3 10 ml). The product obtained was dried in an oven at 808C for 12 h to give 0.50 g pale yellow powder in 68.5% yield. This is a typical procedure and for preparation of other samples, see Table 1.

Table 1 Reagent amounts for different samples PS-DVB (g) 6a 6b 6c 6d 0.51 0.26 0.13 0.06 N -Phthaloyl L-leucine acid chloride ( 4 ) (g) 0.25 0.25 0.25 0.25 AlCl 3 (g) 0.48 0.48 0.48 0.48 1,2-Dichloroethane (ml) 8 8 8 8

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Table 2 Elemental analyses and isolated yield of samples 6a 6d Mol ratio a Primary PS-DVB 6a 6b 6c 6d
a b

C% 91.88 86.47 83.97 87.01 80.12

H% 7.84 7.61 7.09 7.37 7.10

N% 0.90 0.64 0.26 0.09

Yield (%)b 68.5 56.3 28.6 17.9

5 2.6 1.3 0.6

Mol ratio of PS-DVB repeating unit to N -phthaloyl L-leucine acid chloride. Measured by gravimetry.

N -Phthaloyl L-leucine acid chloride ( 4 ) was used as the chiral acylating agent of PS-DVB via FriedelCrafts acylation. If the amino group in L-leucine ( 2 ) is not protected during its conversion to acid chloride, it will be polymerized through the condensation polymerization of free amino group of one molecule and the newly formed acyl chloride group of the other molecule. Therefore we are obliged to protect the amino group rst and then prepare the acid chloride ( 4 ). FriedelCrafts acylation proceeded in the presence of aluminum chloride as the Lewis acid catalyst and 1,2-dichloroethane as the solvent. The reaction progresses rapidly, usually requiring no more than 2 h. It was experienced that at reaction times greater than 2 h, decomposition or degradation occurs and the total yield markedly decreases. Also it is notable that the reaction should be performed at ambient temperature to protect the resin from over swelling and correspondingly crushing. At rst, the optically active acid chloride ( 4 ) was dissolved in 1,2-dichloroethane and the temperature reached 08C. PS-DVB powders were added to this solution and stirred for 30 min. Then AlCl 3 was added slowly to the above mixture at 08C. The reaction mixture color turned from yellow to brown after 30 min stirring which conrms the progress of reaction at this temperature. After 60 min stirring at 08C, the reaction temperature was raised to room temperature. The products were puried according to the procedure mentioned in the Experimental section. The color of modied PS-DVB beads was

yellow after drying at 808C for 12 h. This change in color of primary PS-DVB and modied product is due to the bonding of a carbonyl group to the phenyl ring of polystyrene which varies the absorption band of the newly made product. Also it may be related to the linkage of acid chloride which is yellow in color and gives its color to the corresponding product. The schematic mechanism of the above reaction is demonstrated in Scheme 2. Washing with 10% HCl solution separates the aluminum chloride bonded to the oxygen atom of the carbonyl group ( 5 ). The FT-IR spectrum of the nal product ( 6a) shows the progress of the reaction (Fig. 1). The peak at 1764 cm 2 1 is related to asymmetrical C=O stretching and the peak at 1711 cm 2 1 belongs to symmetrical C=O stretching of imid groups [27]. The carbonyl peak of ketone group at 1711 cm 2 1 is overlapped with the symmetrical C=O stretching broad band of the imid group.

Scheme 2.

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Fig. 1. FT-IR spectra of original PS-DVB (- - -) and modied PS-DVB ( 6a) ().

It is also notable that the unreacted acid chloride is soluble in 1,2-dichloroethane and is ltered off during the rst step of the work-up. However, those that might be adsorbed on the polymer particles will be removed in washing with acid and base. Therefore, FT-IR analysis results conrm the progress of reaction qualitatively. Because of the insolubility of the modied and cross-linked PS-DVB ( 6 ), the percentage of nitrogen measured by elemental analysis identies the quantitative amount of functionality. This value is a useful scale of functionalization and has been extensively applied before [1113,28]. Four samples ( 6a 6d ) were prepared with different mol ratios of PSDVB repeating unit to N -phthaloyl L-leucine acid chloride ( 4 ). The data available in Table 2 show that with the increase in acid chloride amount (decrease in mol ratio) under similar conditions, the amount of functionalization and total yield is decreased. This phenomenon could be explained due to the characteristics of ionic polymers. Polymers bearing ionic groups bound to the backbone have been shown to exist in solution with extensive ionic clustering [29]. The presence of such domains would be ex-

pected to lead to restricted mobility of polymer chains, while simultaneously providing regions of high concentrations of functional groups [30]. According to Scheme 2, modied polymer ( 5 ) is produced during the progress of the reaction. So the ionic character of the product ( 5 ) will result in clustering of the swelled PS-DVB and consequently decrease the amount of modication and total yield. It should be noted that the yield of FriedelCrafts acylation was measured by gravimetry and shows that a moderately good level of modication has occurred. Also the variation of modication due to the nitrogen percentage in the nal product versus mol ratio is shown in Fig. 2.

4. Conclusion The main purpose of this study was to prepare chiral polymers by supporting N phthaloyl L-leucine acid chloride on the copolymer of styrenedivinylbenzene beads via FriedelCrafts acylation reaction. These modied polymers have the potential of being used as polymer supported chiral stationary phase.

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Fig. 2. Variation of mol ratio of PS-DVB to acyl chloride 4 versus incorporated nitrogen (%).

FT-IR and elemental analysis of the products obtained conrm the progress of the reaction. So we have succeeded in preparing optically active poly(styrenedivinylbenzene) copolymers which could be used as the packing for columns in chromatography. The next step is to apply this chiral stationary phase for the separation of enantiomers from racemic mixtures and these results will be reported in future.

Acknowledgements A.R.M. thanks M. Parvazinia for his helpful contribution. I also wish to express my gratitude to the Iran Polymer Institute for nancial support of this work, grant No. 798 CH 375.

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