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Reactive & Functional Polymers 50 (2002) 217–223www.elsevier.com/locate/react A facile and efficient method for preparation of chiral supported

Reactive & Functional Polymers 50 (2002) 217–223 www.elsevier.com/locate/react A facile and efficient method for

www.elsevier.com/locate/react

A facile and efficient method for preparation of chiral supported poly(styrene–divinylbenzene) 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 efficient method for preparation of optically active poly(styrene–divinylbenzene) copolymers (PS-DVB) is presented here. This is carried out by Friedel–Crafts 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 confirm that the above modification 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(styrene–divinylbenzene) copolymer; N-Phthaloyl L-leucine acid chloride; Chiral supported polymers; Friedel–Crafts acylation; Functional polymers

1. Introduction perform electrophilic aromatic substitution re- actions such as nitration and sulfonation [4–6].

During the last few decades, special attention have been paid to synthesis of partially func- tionalized polystyrene [1–3]. This is due to the low cost and wide applicability of this polymer. Chemical modification of resins based on poly- styrene has been studied increasingly, because the aromatic ring of styrene group could easily

FriedelCrafts acylation on polystyrene is another attractive subject that has been used for different systems, such as preparation of re- agents [7–10], ion-exchange resins [11–13] and also development of thermal properties homo- polymers and copolymers of polystyrene [14

16].

*Corresponding author. Tel.: 1 98-21-602-6317; fax: 1 98-21-

602-6500.

E-mail address: a.mahdavian@proxy.ipi.ac.ir (A.-R. Mahda- vian).

The past 30 years have experienced an ex- ponential growth in the rational design of methods for stereoisomer separation. The first 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

1381-5148/02/$ – see front matter PII: S1381-5148(01)00109-2

2002 Elsevier Science B.V. All rights reserved.

218 A.-R. Mahdavian, S. Khoee / Reactive & Functional Polymers 50 (2002) 217 223

of separations could be divided into two

categories: (i) synthetic polymers such as chiral

stationary phase and (ii) polymer

chiral stationary phase. The supported polymers with chiral groups are based on inorganic polymers such as silica [1820] or organic

polymers such as polystyrene [21–24]. 10 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 (iso- thermal 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

Friedel–Crafts acylation in a direct reaction. stirred for 5 h. Then it was filtered off, washed

with distilled water and dried. The beads ob- tained were sieved to separate the 200–400 2. Experimental mesh portion. This part was suspended in 10% aqueous solution of HCl (v/v) and stirred for 1

2.1. Materials

h at 508C. Then it was filtered, washed with distilled water and dried at 808C for 12 h.

Fluka. Styrene monomer was received

Tabriz Petrochemical Inc., Iran. Styrene and

divinyl benzene were washed with 5% solution

NaOH/water (w/v) and distilled water, respec-

tively to remove inhibitors and then stored

08C before use. All other reagents were used

without purification.

The water bath temperature was 708C and the reaction vessel equipped with thermometer, nitrogen gas inlet, etc. were placed in it; 9.2 3

2.3. Suspension polymerization of styrene- divinyl benzene

supported

23

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 Friedel–Crafts acylation reaction of the above-mentioned acid chloride with poly(styrene–divinylbenzene) co- polymer to produce chiral stationary phase which could be used as packing in column chromatography. To our knowledge, this is the first report of preparation of chiral polymers via

Reagents were purchased from Merck and

from

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

at

2.2. Equipment

Suspension polymerization was performed using a glass reactor, steel water bath, controll- able speed motor equipped with three curved blades and flat-type steel baffle. Infrared spectra were recorded on a Bruker- IFS 48 FT-IR spectrophotometer. Spectra of solids were obtained using KBr pellets. Vibra- tional transition frequencies are reported in wavenumber (cm ). Elemental analyses were run by a CHN-O-RAPID Heraeus, GMBH instrument.

21

in wavenumber (cm ). Elemental analyses were run by a CHN-O-RAPID Heraeus, GMBH instrument. 2 1

Scheme 1.

A.-R. Mahdavian, S. Khoee / Reactive & Functional Polymers 50 (2002) 217 223

219

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

3

25

D

2.5. FriedelCrafts acylation of N-phthaloyl

L-leucine acid

(typical procedure)

chloride (4) with PS-DVB

24

A 0.25-g aliquot (8.94 3 10 mol) of chiral acid chloride (4) was dissolved in 8 ml 1,2- dichloroethane at room temperature in a 25-ml round-bottomed flask. 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 tempera-

3. Results and discussion

Beads of poly(styrene–divinylbenzene) co-

polymer (PS-DVB) from 200–400 mesh were used in this work. The PS-DVB copolymer prepared by suspension polymerization contains a small amount of adsorbed poly vin- ylpyrolidone (PVP) as stabilizer. On the other hand, functionality of PS-DVB beads is de-

termined 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 modi- fication of PS-DVB via Friedel–Crafts acyla- tion. 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

in aqueous phase. The

above mixture was filtered off and washed with plenty of water until the filtrate 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.

23

ture and then 0.48 g (3.58 3 10 mol) AlCl beads are dissolved

3

was added portion-wise to this mixture. After 60 min stirring at 08C, the temperature of the reaction mixture was raised to room tempera- ture. The reaction was carried out for 2 h and then it was filtered off. Washing of the obtained product was performed according to the follow-

ing procedure: (i) 10% aqueous solution of HCl N-Phthaloyl L-leucine acid chloride (4) was

prepared according to the steps shown in Scheme 1. N-Phthaloyl L-leucine (3) is syn- thesized from the condensation reaction of L- leucine (2) as a chiral amino acid and phthalic

anhydride (1) in the presence of triethylamine.

acid

yellow powder in 68.5% yield. After further purification, the carboxylic

(3) was converted to the corresponding acid

tion of other samples, see Table 1. chloride (4) in the presence of thionyl chloride.

(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

This is a typical procedure and for prepara-

Table 1 Reagent amounts for different samples

 

PS-DVB (g)

N-Phthaloyl L-leucine acid chloride (4) (g)

AlCl

3

(g)

1,2-Dichloroethane

   

(ml)

6a

0.51

0.25

0.48

8

6b

0.26

0.25

0.48

8

6c

0.13

0.25

0.48

8

6d

0.06

0.25

0.48

8

220 A.-R. Mahdavian, S. Khoee / Reactive & Functional Polymers 50 (2002) 217 223

Table 2 Elemental analyses and isolated yield of samples 6a6d

 

Mol ratio

a

C%

H%

N%

Yield (%)

b

Primary PS-DVB

91.88

7.84

6a

5

86.47

7.61

0.90

68.5

6b

2.6

83.97

7.09

0.64

56.3

6c

1.3

87.01

7.37

0.26

28.6

6d

0.6

80.12

7.10

0.09

17.9

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

N-Phthaloyl L-leucine acid chloride (4) was used as the chiral acylating agent of PS-DVB via Friedel–Crafts acylation. If the amino group in L-leucine (2) is not protected during its conversion to acid chloride, it will be polymer- ized 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 schematic mechanism of the above re-

action is demonstrated in Scheme 2. Washing

the amino group first and then prepare the acid

chloride (4). with 10% HCl solution separates the aluminum

Friedel–Crafts acylation proceeded in the presence of aluminum chloride as the Lewis

acid catalyst and 1,2-dichloroethane as the The FT-IR spectrum of the final product (6a)

solvent. The reaction progresses rapidly, usually requiring no more than 2 h. It was experienced that at reaction times greater than 2 h, decompo- sition or degradation occurs and the total yield markedly decreases. Also it is notable that the reaction should be performed at ambient tem- perature to protect the resin from over swelling and correspondingly crushing. At first, 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 was added slowly to the above mixture at 08C. The reaction mixture color turned from yellow to brown after 30 min stirring which confirms the progress of reaction at this temperature. After 60 min stirring at 08C, the reaction temperature was raised to room temperature. The products were purified accord- ing to the procedure mentioned in the Ex- perimental section. The color of modified PS-DVB beads was

chloride bonded to the oxygen atom of the carbonyl group (5).

yellow after drying at 808C for 12 h. This change in color of primary PS-DVB and modi- fied 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.

shows the progress of the reaction (Fig. 1). The peak at 1764 cm is related to asymmetrical C=O stretching and the peak at 1711 cm belongs to symmetrical C=O stretching of imid groups [27]. The carbonyl peak of ketone group at 1711 cm is overlapped with the symmetri- cal C=O stretching broad band of the imid group.

21

21

21

is overlapped with the symmetri- cal C = O stretching broad band of the imid group.

Scheme 2.

3

A.-R. Mahdavian, S. Khoee / Reactive & Functional Polymers 50 (2002) 217 223

221

& Functional Polymers 50 (2002) 217 – 223 221 Fig. 1. FT-IR spectra of original PS-DVB

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

pected to lead to restricted mobility of polymer chains, while simultaneously providing regions of high concentrations of functional groups [30]. According to Scheme 2, modified 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 conse- quently decrease the amount of modification and total yield. It should be noted that the yield of Friedel–Crafts acylation was measured by gravimetry and shows that a moderately good level of modification has occurred.

functionalization and has been extensively ap- Also the variation of modification due to the

nitrogen percentage in the final product versus mol ratio is shown in Fig. 2.

plied before [11–13,28]. Four samples (6a6d) were prepared with different mol ratios of PS- DVB 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 The main purpose of this study was to

prepare chiral polymers by supporting N- phthaloyl L-leucine acid chloride on the co- polymer of styrene–divinylbenzene beads via Friedel–Crafts acylation reaction. These modi- fied polymers have the potential of being used as polymer supported chiral stationary phase.

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-

It is also notable that the unreacted acid chloride is soluble in 1,2-dichloroethane and is filtered off during the first 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 confirm the progress of reaction quali- tatively. Because of the insolubility of the modified and cross-linked PS-DVB (6), the percentage of nitrogen measured by elemental analysis identifies the quantitative amount of functionality. This value is a useful scale of

4. Conclusion

222 A.-R. Mahdavian, S. Khoee / Reactive & Functional Polymers 50 (2002) 217 223

Reactive & Functional Polymers 50 (2002) 217 – 223 Fig. 2. Variation of mol ratio of

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 confirm the progress of the reaction. So we have succeeded in preparing optically active poly(styrene–divinylbenzene) 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. [9]

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Acknowledgements

A.R.M. thanks M. Parvazinia for his helpful

contribution. I also wish to express my gratitude

nancial sup-

to the Iran Polymer Institute for

port of this work, grant No. 798 CH 375.

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