Buletinul tiinific al Universitii Politehnica din Timisoara, ROMNIA Seria CHIMIE I INGINERIA MEDIULUI Chem. Bull. "POLITEHNICA" Univ.

(Timioara)

Volume 51(65),2006

Solubility and viscosity studies on inulin modified with methacyloyl and palmitoyl chlorides
Gerlinde Rusu *, G. Bandur *, I. Manoviciu *, L. Rusnac *, Nicoleta Plesu **
*

Politehnica University of Timisoara, Industrial Chemistry and Environmental Engineeri ng Faculty, Piata Victoriei 2, 30006, Timisoara, Romania Phone: (40) 0256 -404215, Fax: (40) 0256-404240, E-Mail: gerlinde.grandtner@chim.upt.ro
**

Institut of Chemistry, Romanian Academy, Timisoara, Mihai Viteazul 24, Romania

Abstract: Inulin was modified in order to obtain mixed esters. The modification was carried out with methcryloyl chloride in a first step, followed by an acylation with palmitoyl choride in the second step. After the isolation and the drying of the esters, several solutions with different concentrations were prepared in order to perform viscometric measurements. The solvent used in the determinations was chosen after calculating the solubility parameter for the esters and for se veral other solvents. The intrinsic viscosity was determined at different temperatures with two methods: Solomon-Gateaman method and the Huggins method. Keywords: inulin, inulin mixed ester, solubility parameter, and intrinsic viscosity The degree of polymerization (DP) of inulin (n,m) varies from 2 to 70 and mainly depends on the type of plant from which it is isolated, on the weather conditions during the growth, and on the physiological age of the plant [6]. The most important sources of inulin are Cichorium intybus (chicory), Dahlia pinuata CaV. (dahlia), and Helianthus tuberosus (Jerusalem artichoke) which have an average DP of 10 -14, 20, and 6, respectively [7]. Recently, many efforts have been devoted to the chemical modification of inulin in order to develop industrial products based on renewable resources and with specific characteristics [8]. Among these products are the inulin esters. In this article , some new mixed inulin esters were prepared by the modification of inulin with methcryloyl chloride in a first step, followed by an acylation with palmitoyl choride in the second step . The study of polymer solutions provides with the valuable information on the molecular lev el. Viscosity seems to be one of the widely studied properties and the measurements of the viscosity coefficient can provide us with a great deal of very useful information, especially about the dimension of polymer molecules (from intrinsic viscosity) and interactions between the polymer chains and molecules of solvent (from viscometric constant) [9]. The solution forming capacity of the polymer is determined by the following factors [10]: - polymer and solvent nature; - flexibility of the macromolecular cha ins; - molecular mass of the polymer; - chemical composition of the polymer; - polymer crystallinety; - cross-link state; - temperature; The solubility relationships for the macromolecular systems are more complex than for the small molecules, although some empirical solubility rules (deduced from

1. Introduction
Most synthetic polymers are designed and manufactured to withstand environmental degradation. In general, these materials have a sho rt useful life, in many cases less than two years. These two facts have led, in recent years, to a significant increase in the amount of plastic waste [1] . To solve this problem, the synthesis of biodegradable plastics by copolymeriyation of usual monomers with biopolymers such as polysaccharides is taken in consideration. Inulin is a polydisperse polysaccharide consisting mainly, if not exclusively, of (2-1) fructosyl fructose units (Fm) with normally, but not necessarily, one glucopyranose unit at the reducing end (GF n)[2,3] (Fig. 1). It is also known that the fructose molecules in the GFn form are all present in the furanose f orm. Only in the Fm forms, the ending and reducing fructose is in the pyranose form [4] . Further studies on the structure of inulin showed that inulin is a slightly branched fructan: the amount of (2-6) branches in chicory and dahlia inulin is 1-2% and 4-5%, respectively [5].

Fig. 1. The structure of inulin

Chem. Bull. "POLITEHNICA" Univ. (Timioara)

Volume 51(65),2006

the small molecule behavior) can be applied for the polymers: - The solubility is favored by the chemical and structural propinquity; the polymer solvent affinity is maximal, when the two molecules have the same polarity; - The solubility decreases as the molecular mass grows; In this paper the intrinsic viscosity of some new inulin mixed esters was determined using methyl methacrylate solutions with four different concentrations of three different inulin mixed esters . Due to the presence of double bonds in the structure of these mixed esters, they can be used furthermore in copolymerization processes with acrylic monomers in order to obtain biodegradable products. Practically, the prediction of intrinsic viscosity in polymer solutions is important for the evaluation of the domain of applicability that defines the area of reliable predictions .

inulin methacrylate, because this compound was still soluble in water, and the second, the fact that the long alkyl chain acts as an inter plasticizer. 2.3 Determination of the solubility parameter For the three inulin esters the solubility parameter was calculated using the Van Krevelen atomic attraction constants and the following equation [8]:

(1) M where: is the solubility parameter, is the density, M is the molecular mass and Fi sum of the atomic attraction constant (after Van Krevelen) . In order to calculate the solubility parameter the density must be known. The density was determined using KERN PRJ 6203 M equipment. 2.4 Viscometry The viscometric measurements were performed on the inulin esters in MMA solutions. Four solutions with different concentration (0.02, 0.03, 0.04, 0.06 g/mL) were prepared. Viscometric measurements were carried out using an Ostwald viscometer. The temperature was regulated by a circulating bath (30 and 40C). At 20C the esters did not solve properly in any solvent and these measurements were not taken into consideration.

F i

2. Experimental
2.1 Materials Chicory inulin (Aldrich, average degree of polymerization n = 10), N,N-dimethylacetamide (DMAc) (Merck), N,N-dimethyl-4-aminopyridine (DMAP) (Merck), methacryloyl chloride (MC l), (Fluka), palmitoyl chloride (PCl) (Merck), carbon tetrachloride (Merck), methyl methacrylate (MMA) (Merk). All this materials were used as received. 2.2 Ester Synthesis Inulin and DMAP (3 Eg/fructose unit) were dissolved in 20 mL DMAc. First, MCl (1 Eg/fructose unit) was added and the reaction mixture was stirred for 1 hour at room temperature when PCl (1, 1.5 and 2 Eg/fructose unit) was added. One hour later distillated water (60 mL) was added to neutralize the amount of acid chlorides, which had not reacted. The isolation of the inulin esters was carried out by separation with carbon tetrachloride (20 mL) and water. There were several separations for a better purity of the esters. The products were dried first at room temperature and then under vacuum at 50C. Table 1 presents the synthesized inulin esters.
TABLE 1 The synthesized inulin esters

3. Results and Discussions

The solubility parameter point out theoretically if the esters can be solved in the solvent. The solubility parameter for synthesized inulin esters and for some solvents was calculated based on equation (1). The calculated solubility parameters are presented in Table 2. As solvents methyl methacrylate (MMA), styrene (S) and toluene (T) were chosen.
TABLE 2. The density, the calculated molecular mass, the atomic attraction constant and the solubility parameter for the three inulin mixed esters and solvents

[g/cm3]

M [g/mol]

Fi
[(cal/cm ) /mol]
3 1/2

E1 E2 E3

Inulin [g] 2 2 2

DMAP [g] 4.52 4.52 4.52

DMAc [mL] 20 20 20

MCl [mL] 1.2 1.2 1.2

PCl [mL] 3.8 5.6 7.5

E1 E2 E3 MMA S T

1.129 1.064 1.048 0.943 0.909 0.865

468 n 587 n 706 n 100 104.15 92.14

3516 n 4490.25 n 5464.5 n 947 1027 947

8.48 8.14 8.11 8.93 8.96 8.89

The reason why MCl was used is the fact that these esters will be used forward in several polymerization processes where a double bond is required. PCl was used mainly for two reasons: first to change the solubility of

It can be seen that these values are neighboring for all the three solvents and inulin esters. Based on the value of the solubility parameter and due to its chemical

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Volume 51(65),2006

[n] (ml/g)

structure MMA is the most similar to the inulin esters and it was chosen for viscosity determination. In order to do that, solutions with different concentrations were prepared. The intrinsic viscosity was determined using two methods: Solomon -Gateaman method and the Huggins method.

30
18 16 14 12 10 8 6 4 2 0 0 0.001 0.002 0.003 0.004 0.005 0.006 0.007 c (g/ml)

EP1 EP2 EP3

3.1 Solomon-Gateaman Method The Solomon-Gateaman method is an empirical one based on the following equation: (2) c where [] is the intrinsic viscosity; sp the specific viscosity rel the relative viscosity and c the concentration.

a)
40
16 14 12 10 8 6 4 2 0 0 0.001 0.002 0.003 0.004 0.005 0.006 0.007 c (g/ml)

[ ]

2( sp

ln rel )

[n] (ml/g)

EP1 EP2 EP3

rel

(3)

0 where is the solution viscosity and 0 is the solvent viscosity. (4) sp rel 1
As long as all determinations were performed on the same Ostwald viscometer, rel is in fact the ratio of the the flow times (of the solution and of the solvent). The values for the intrinsic viscosity calculated from (2) are presented in table 3.
TABLE 3. The intrinsic viscosity values for the inulin mixed esters calculated using the Solomon -Gateaman equation.

b)
Fig 2. The intrinsic viscosity variation with the concentration for the inulin esters solutions at 30 (a) and 40C (b)

3.2 Huggins Method Huggins method is an alternative method for the intrinsic viscosity determination. This method uses the following equation:

c [g/mL] E1 0.00221 0.00305 0.00401 0.00603 30C 8.70 10.36 11.65 13.23 40C 8.03 8.80 9.57 12.82

[] [ml/g] E2 30C 40C 9.33 8.61 10.50 9.69 12.32 10.18 14.31 13.52

E3 30C 10.88 11.56 12.96 15.34 40C 10.05 10.68 11.90 14.50

From table 3 it can be seen that the intrinsic viscosity values increases as the concentration increase. Fig. 2 presents the plot of the intrinsic viscosity towards the concentration. The intrinsic viscosity grows linearly with the concentration. Also, from table 3 it can be notice d that at 30C E1 has the lowest intrinsic viscosity value while E3 had the highest. The E2 intrinsic viscosity value is between these two limits. It can be concluded that the intrinsic viscosity grows with the acylation degree. At 40C the inulin esters solutions show similar pattern.

2 (5) [ ] H c where sp is the specific viscosity, c the concentration, kH the Huggins constant. For this method, a graphical representation sp /c vs. c, is necessary (sp is the specific viscosity and c is the concentration). Extrapolation of the curve to c=0, gives the intrinsic viscosity. Fig. 3 exemplifies the procedure for E2 at 40C and Table 4 presents all the results. [ ] k

sp

sp/c 16 14 12 10 8 6 4 2 0 0 0.002

EP2-40

y = 1269.7x + 6.6577 R2 = 0.9882

0.004

0.006 0.008 c[g/ml]

Fig.3. Graphical representation of the Huggins method for

E2 at 40C

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Chem. Bull. "POLITEHNICA" Univ. (Timioara) TABLE 4 The intrinsic viscosity values for the inuli n esters calculated with Huggins equation

Volume 51(65),2006

[] [ml/g]

E1 E2 E3

30C 6.96 7.53 7.89

40C 6.38 6.65 7.11

The ester E1, which has the lowest intrinsic viscosity, is followed by ester E2 and ester E3 , the last having the highest intrinsic viscosity. These results are similar with that obtained b y the former method: the intrinsic viscosity grows with the acylation degree.

determination of the intrinsec viscosity because its chemical structure is appropriate to those esters. The intrinsic viscosities determined by Huggins method are lower than those obtained by the SolomonGateaman method. It can be also seen that the values determined by both methods grow from E1 to E3, E2 having an intermediary value, as the acylation degree increase. It can be also seen that the intrinsic viscosity increase linearly with the boost of the concentration.

REFERENCES
1. X. Ramis, A. Cadenato, J.M. Salla, A. Valles, L. Contat, A. Ribes, Polymer Degradation and Stability, 86, 2004 pp.483491 Hirst E. L., McGilvray D. I., Percival E. G. V., J. Chem. Soc. 1950, 1297. De Leenheer L., Hoebregs H., Starch 1994, 46, p. 193 De Leenheer L., Van Bekkum H., Roper H., Voragen A. L. J., In Carbohydrates as Organic Raw Materials III; Eds. CH: Weinheim, 1996; p 67. De Leenheer L., Van Bekkum H., Roper H., Voragen A. L. J., In Carbohydrates as Organic Raw Materials III; Eds. CH: Weinheim, 1996; p 67. W. Beck, R. H. F. Nitsch, J. Chromatogr. 1984, 303, p. 417. Christian V. Stevens, Alessia Meriggi, Karl Booten, Biomacromolecules, 2, 1, 2001 p. 1 I. Mindru, M. Leca, Chimia macromoleculelor si a coloizilor, Editura didactica si pedagogica, 1977, p. 216 A. Tager, Physical Chemistry of Polymers, Min Publ. Moscow, 1972

4. Conclusions
A new family of inulin esters was prepared with a simple method. For these esters, the solubility parameter was calculated by means of the Van Krevlen atom attraction values; their intrinsic viscosities were determined by two different methods. The solubility parameter calculated for the synthesized esters are 8.48, 8.14 and 8.11 for E1, E2 and E3 respectively. The calculated solubility parameter indicates that MMA, styrene and toluene solved properly the esters. The MMA was chosen as solvent for the

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