European Polymer Journal 46 (2010) 11511157

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European Polymer Journal

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Synthesis and biodegradation studies of new copolymers based on sucrose derivatives and styrene
M. Teresa Barros a,*, Krasimira T. Petrova a,*, Raj P. Singh b
a b

REQUIMTE, CQFB, Departamento de Qumica, Faculdade de Cincias e Tecnologia,Universidade Nova de Lisboa, 2829-516 Caparica, Portugal Polymer Sci. & Engg. Division, National Chemical Laboratory, Pune 411008, India

a r t i c l e

i n f o

a b s t r a c t
Novel unsaturated esters of sucrose were synthesised directly and in good yields from sucrose using a simple, mild, and selective Mitsunobu procedure. These regioisomerically pure vinyl sugars have been copolymerised with styrene by a free radical process, yielding unbranched linear polymer materials with pendant sucrose moieties. Their physical properties indicate that these polymers have potential technological relevance as amphiphilic and biodegradable materials. Biodegradation tests on the copolymer samples by a fungal (Aspergillus niger) culture method showed a fungal growth P60%, indicating good biodegradability and that the copolymers were partially bio-assimilated during microbial attack. 2010 Elsevier Ltd. All rights reserved.

Article history: Received 15 September 2009 Received in revised form 31 January 2010 Accepted 3 February 2010 Available online 18 February 2010 Keywords: Vinyl sucrose ester monomers Biodegradable copolymers Free radical copolymerization Biodegradation culture test

1. Introduction The demand for biodegradable plastics has increased over the past few decades, not only due to increasing environmental concerns, but also for biomedical applications [1]. Sucrose is a low molecular weight renewable carbohydrate feedstock from which it is possible to elaborate new materials [2], such as water-soluble and/or amphiphilic, biocompatible polymers [3] and other new compounds due to its low price. The synthesis and applications of different sucrose esters has been reported [410]. Since sucrose has eight chemically active hydroxyl groups, regioselective derivatisation is important for the selective synthesis of sucrose-containing linear polymers [11,12]. Protectiondeprotection strategies have been discussed by Jarosz et al. [13]. Using sugar functionalised petrochemical polymers such as polystyrene for use as biodegradable polymers is a recently discovered application of a sugar linked synthetic polymer [14]. The class of sugar based polymers,
* Corresponding authors. Tel.: +351 212948300; fax: +351 212948550. E-mail addresses: mtbarros@dq.fct.unl.pt (M.T. Barros), krasimira. petrova@dq.fct.unl.pt (K.T. Petrova), rp.singh@ncl.res.in (R.P. Singh). 0014-3057/$ - see front matter 2010 Elsevier Ltd. All rights reserved. doi:10.1016/j.eurpolymj.2010.02.002

generally known as poly(vinylsaccharide)s, have also been investigated for a variety of applications, particularly in the biomedical eld [15,16]. The most widely used method for the synthesis of poly (vinylsaccharide)s has been based on free radical polymerisations of vinyl sugars [17]. For an extensive review on the preparation and applications of this type of polymers, see [18] and references therein. Our approach was to introduce polymerisable carbohydrate containing moieties into polyvinyl chain polymers [7,8,19]. There has been a worldwide realisation that nature derived monosaccharides, disaccharides, oligosaccharides and polysaccharides can provide the raw materials needed for the production of numerous industrial consumer goods [1,20]. The present investigation was also intended to study the extent of biodegradability of poly(vinyl saccharide ester)s under culture incubation. Mitsunobu esterication conditions [21] are known to provide good selectivity, even in the case of a complex polyol like sucrose, thus allowing a rapid and efcient synthesis of sucrose esters. Although the atom economy of the procedure was poor, it gave excellent results on a small scale and allowed us to avoid the use of protecting group chemistry and multi-step procedures. The regioselectivity of the Mitsunobu reaction towards 6-O-monoesters and

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6,60 -O-di-esters of sucrose has been documented earlier [22,23], and we explored its application for obtaining unsaturated monomers capable of polymerizing. Herein, the synthesis of novel unsaturated sucrose esters by reacting sucrose with unsaturated carboxylic acids under Mitsunobu conditions is presented (Scheme 1), as well as their successful free radical copolymerisation with styrene (Scheme 2). Some physical properties of the resulting polymeric materials are also reported. 2. Synthesis of unsaturated sucrose esters The procedure adopted was based on the Mitsunobu reaction [21] as a convenient method for selective esterication to afford mono- and di- esteried products (Scheme 1). To a solution of sucrose in dry DMF, triphenylphosphine and the corresponding acid were added, and cooled to 0 C. Diisopropyl azodicarboxylate (DIAD) was added slowly, and the mixture was stirred at room temperature for 24 h (see SI). In order to obtain the sucrose monoesters the reaction was monitored by TLC, and it was stopped when the di-esters were detected. Thus, it was possible to optimise the yields of regioisomerically pure unsaturated monoesters of sucrose. The differentiation between the regioisomeric esters of sucrose can be veried by several methods [25,26]. However, the assignment was normally made by HMBC NMR experiments [27]. Thus, a crosspeak between the C of the carbonyl group and H-6 was observed, conrming the position of the substituent at C-6, as well as the longer range couplings between C-4 and H-6, between C-6 and H-4, and C-5 and H-6, which were consistent with structures 14. The sucrose 6,60 -O-di-esters were isolated in smaller amounts and it was not possible to avoid their formation. The presence of other possible side products such as anhydro derivatives was not observed [22]. The Mitsunobu reaction applied to sucrose and acrylic acids is selective for the 6-position, unlike the corresponding silylation reaction with bulky silyl reagents such as TBDPSCl, which is regioselective for the 60 -position

R1 HC n CH2 O O

R2 O OR OR O O OR OR OH AIBN

RO + m RO

HC CH2

R2 HC O n (S)

R1 C
O m

1: R=H, R1=CH3, R2=H 2: R=H, R1=H, R2=CH3 3: R=Ac, R1=CH3, R2=H 4: R=Ac, R1=H, R2=CH3

Scheme 2. General scheme for the free radical copolymerisation of monomers 14 with styrene.

[28]. The reason for this differentiation is probably determined during the reaction of the pentavalent phosphorus complex, formed between triphenyl phosphine and DIAD, with the primary hydroxyls of the sucrose molecule [29,30]. Subsequent conventional acetylation afforded the corresponding acetylated products in quantitative yields. The monomers obtained were not stable and tended to polymerise spontaneously upon concentration. This difculty was overcome by adding hydroquinone to the mixture for storage and which was removed by ash column chromatography prior to the copolymerisation experiments [24]. Two useful measures of the potential environmental acceptability of chemical processes are the E factor, dened as the mass ratio of waste to desired product, and the atom utilization, calculated by dividing the molecular weight of the desired product by the sum of the molecular weights of all substances produced in the stoichiometric equation [31]. For mono-esterication of sucrose by Mitsunobu procedure these values are as follows: E factor = 2.35; Atom utilization = 46%. In this calculation the solvent DMF was

OH HO HO O OH

OH O O OH OH OH

RCOOH, DIAD, PPh3 DMF, r.t., 24 h R: H2C=C(CH3)H3CCH=CHR

R O HO HO O O OH O OH OH OH Ac2O, py, r.t. O

O O AcO

OAc O O OAc OAc

OH O

AcO AcO

OAc

1: R= H2C=C(CH3)-, 49% 2: R= H3CCH=CH-, 51%

3: R= H2C=C(CH3)-, 48% 4: R= H3CCH=CH-, 50%

Scheme 1. Sucrose esterication under Mitsunobu conditions, and subsequent peracetylation of the products.

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not taken into consideration as waste as it was easily recovered and reused. According to the study presented by Sheldon in [31], these values are in the range reported for bulk chemicals, and are much lower than for ne chemical industry. They show that the presented one-step method for valorization of sucrose as renewable natural feedstock is benecial over multistep protectiondeprotection strategies. 3. Synthesis of amphiphilic copolymers copolymerisation of vinyl sugar monomers 14 with styrene by free radical polymerisation The copolymerisation of monomers 14 with styrene (Scheme 2) has been examined in the presence of AIBN, as free-radical initiator, in DMF as a solvent for 1 and 2, and toluene for 3 and 4, at 70 C under Ar atmosphere, followed by precipitation with cold ethanol. The ltration and washing of the precipitate with EtOH, and repeated dissolution and reprecipitation, assured the removal of unreacted monomers, as they were soluble in EtOH. GPC afforded monomodal distributed chromatograms, which suggested the existence of copolymers. As a rst approach to the desired materials, a study of copolymerisation as a function of the reaction time (6 30 h) was carried out (Tables 13), with an initial mol ratio in all experiments [sug]/[st] = 0.1. The results showed that optimum polymer properties (highest average molecular

weights) were obtained after 24 h, and all further experiments were conducted over this reaction period (see SI, Figs. 1 and 2). The rate of incorporation of the sugar monomer was studied by variation of the initial sugar/styrene mol ratio over the range 0.051 under the same reaction conditions (Tables 46). The copolymer compositions were determined by 1H NMR by comparing the peak areas of the aromatic protons present in the styrene unit with the 14 sucrose unit protons. Radical homopolymerisation of 1 and 2 and their copolymerisation with styrene at higher initial sucrose concentrations afforded powdery materials which were insoluble in several solvents (toluene, THF, DMF, DMSO, and water were tested, stirring at 60 C for 24 h). These results may indicate that they were cross-linked as a result of side reactions. Compound 2, being less reactive in the polymerisation reaction, afforded soluble copolymer samples at lower initial sucrose content. In this case, the maximum sugar incorporation was obtained at an initial mol ratio [sug]0/ [styrene]0 = 0.1, while the overall conversion was inversely proportional to the initial quantity of the sucrose monomer (Table 4). The relation between Mw and the overall conversion versus the initial quantity of the sugar monomer 3 in copolymerisation with styrene (Table 5) was inversely proportional, as expected (Figs. 1a and b). The incorporation of

Table 1 Radical copolymerisation of 6-O-methacryloyl sucrose 1 and styrene as function of time, in DMF as solvent, radical initiator AIBN, 70 C, and under argon atmosphere. No. 1 2 3 4 5
a b c d e f

sug0 a styr0

sug b styr

Time (h) 6 12 18 24 30

Yieldc (%) 49.4 25.0 28.4 19.3 31.3

Mnd (g/mol) 2400 7300 5000 25,900 59,500

Mwd (g/mol) 3400 11,000 7000 38,800 95,300

Mw/Mn 1.4 1.5 1.4 1.5 1.6

de [] 171 304 247 586 904

Df [cm2/s] 2.13 108 1.20 108 1.47 108 6.21 109 4.02 109

0.1 0.1 0.1 0.1 0.1

0.0089 0.028 0.0093 0.014 0.0089

Initial (feed) mol ratio of the monomers. Mole ratio of the comonomers in the copolymer, determined by 1H NMR. Overall conversion of the monomers. Measured by GPC. Effective diameter, determined by light-scattering. Diffusion coefcient, determined by light-scattering.

Table 2 Radical copolymerisation of 6-O-crotonoyl sucrose 2 and styrene as function of time, in DMF as solvent, radical initiator AIBN, 70 C, and under argon atmosphere. No. 6 7 8 9 10
a b c d e f

sug0 a styr0

sug b styr

Time (h) 6 12 18 24 30

Yieldc (%) 12.9 13.7 12.0 24.1 39.3

Mnd (g/mol) 5800 8600 7900 10,700 8500

Mwd (g/mol) 8200 12,500 11,700 17,000 13,100

Mw/Mn 1.4 1.4 1.5 1.6 1.6

de () 824 530 814 528 537

Df (cm2/s) 4.42 109 6.86 109 4.47 109 6.89 109 6.78 109

0.1 0.1 0.1 0.1 0.1

0 0.0036 0.017 0.048 0.0053

Initial (feed) mol ratio of the monomers. Mole ratio of the comonomers in the copolymer, determined by 1H NMR. Overall conversion of the monomers. Measured by GPC. Effective diameter, determined by light-scattering. Diffusion coefcient, determined by light-scattering.

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Table 3 Radical copolymerisation of 10 ,2,3,30 ,4,40 ,60 -hepta-O-acetyl-6-O-methacryloyl sucrose 3 and styrene as function of time, in toluene as solvent, radical initiator AIBN, 70 C, and under argon atmosphere. No. 11 12 13 14 15
a b c d e f

sug0 a styr0

sug b styr

Time (h) 6 12 18 24 30

Yieldc (%) 30.3 21.3 22.0 45.6 61.5

Mnd (g/mol) 4500 9800 43,600 16,300 4100

Mwd (g/mol) 6400 14,700 69,800 26,100 5800

Mw/Mn 1.4 1.5 1.6 1.6 1.4

de () 236 354 770 461 224

Df (cm2/s) 1.54 108 1.03 108 4.73 109 7.90 109 1.62 108

0.1 0.1 0.1 0.1 0.1

0.042 0.017 0.0069 0.013 0.0087

Initial (feed) mol ratio of the monomers. Mole ratio of the comonomers in the copolymer, determined by 1H NMR. Overall conversion of the monomers. Measured by GPC. Effective diameter, determined by light-scattering. Diffusion coefcient, determined by light-scattering.

a
60000 50000 Mw [g/mol] 40000 30000 20000 10000 0

3/styr 4/styr

b
Overall conversion [%].

80 70 60 50 40 30 20 10 0 0 0.5 1

3/styr 4/styr

c 0.7
0.6 [sug]/[syrene] 0.5 0.4 0.3 0.2 0.1 1.5 0 0 0.2 0.4 0.6 0.8 1 1.2

3/styr 4/styr

0.5

1.5

[sug]o/[styrene]o

[sug]o/[styrene]o

[sug]o/[syrene]o

Fig. 1. Molecular weights of the copolymers (a), degree of monomer conversion (b), and degree of incorporation of the sugar monomers copolymers (mole percent) (c) versus initial (feed) mole ratio of monomers.

a 110
100 90 80 70 60 0

3/styrene

b
alpha D

60 50 40 30 20 10 0

optical rotation/ sugar incorporation

Tg

0.02 0.04 [sug]/[styrene]

0.06

0.2

0.4 [sug]/[styr]

0.6

Fig. 2. (a) Glass transition temperatures versus mole percent of incorporation of sugar monomer in the copolymers; (b) Optical rotations versus mole percent of incorporation of sugar monomer in the copolymers.

Table 4 Radical copolymerisation of 6-O-crotonyl sucrose 2 and styrene as function of concentration, in DMF as solvent, radical initiator AIBN, 70 C, and under argon atmosphere. No. 16 17 18
a b c d e f

sug0 a styr0

sug b styr

Time (h) 24 24 24

Yieldc (%) 12.3 24.9 32.9

Mnd (g/mol) 11,200 9500 19,700

Mwd (g/mol) 16,700 14,300 42,600

Mw/Mn 1.5 1.5 2.2

de () 751 678 991

Df (cm2/s) 4.84 109 5.37 109 3.67 109

0.2 0.1 0.05

0.0005 0.0014 0.0006

Initial (feed) mol ratio of the monomers. Mole ratio of the comonomers in the copolymer, determined by 1H NMR. Overall conversion of the monomers. Measured by GPC. Effective diameter, determined by light-scattering. Diffusion coefcient, determined by light-scattering.

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Table 5 Radical copolymerisation of 10 ,2,3,30 ,4,40 ,60 -hepta-O-acetyl-6-O-methacryloyl sucrose 3 and styrene as function of concentration, in toluene as solvent, radical initiator AIBN, 70 C, and under argon atmosphere. No. 19 20 21 22 23
a b c d e f

sug0 a styr0

sug b styr

Time (h) 12 24 24 24 24

Yieldc (%) 54.7 57.5 60.0 68.2 74.5

Mnd (g/mol) 45,200 16,500 20,500 54,500 32,500

Mwd (g/mol) 72,400 26,000 32,700 98,000 55,300

Mw/Mn 1.6 1.6 1.6 1.7 1.7

de () 784 460 518 865 660

Df (cm2/s) 4.64 109 7.90 109 7.02 109 4.21 109 5.51 109

0.1 1 0.5 0.1 0.05

0.048 0.638 0.439 0.076 0.017

Initial (feed) mol ratio of the monomers. Mole ratio of the comonomers in the copolymer, determined by 1H NMR. Overall conversion of the monomers. Measured by GPC. Effective diameter, determined by light-scattering. Diffusion coefcient, determined by light-scattering.

Table 6 Radical copolymerisation of 10 ,2,3,30 ,4,40 ,60 -hepta-O-acetyl-6-O-crotonoyl sucrose 4 and styrene as function of time and concentration, in toluene as solvent, radical initiator AIBN, 70 C, and under argon atmosphere. No. 24 25 26 27 28
a b c d e f

sug0 a styr0

sug b styr

Time (h) 12 24 24 24 24

Yieldc (%) 60.3 13 28 44.0 70.5

Mnd (g/mol) 7800 28,900 28,400 27,700 33,600

Mwd (g/mol) 10,100 43,400 42,500 44,400 57,100

Mw/Mn 1.3 1.5 1.5 1.6 1.7

de () 314 621 615 607 671

Df (cm2/s) 1.16 108 5.86 109 5.92 109 5.99 109 5.42 109

0.1 1 0.5 0.1 0.05

0.051 0.06 0.028 0.016 0.051

Initial (feed) mol ratio of the monomers. Mole ratio of the comonomers in the copolymer, determined by 1H NMR. Overall conversion of the monomers. Measured by GPC. Effective diameter, determined by light-scattering. Diffusion coefcient, determined by light-scattering.

sugar in the copolymer increased with the increasing of the initial ratio [sug]0/[styrene]0 in the range 0.051.0, reaching the greatest value at 0.6 (Fig. 1c). For the copolymerisation of the monomer 4 with styrene (Table 6) the incorporation of sucrose monomer was, on the average, one order of magnitude less then those found when the monomer 3 was used (Fig. 1c). Again, the copolymers, obtained using this procedure, exhibited an inversed variation of Mw and overall conversion with the initial ratio of sucrose monomers/styrene (Fig. 1a and b). The majority of the results obtained for the copolymerisation reactions of the sucrose derivatives 14 showed that copolymers were obtained with a lower incorporation of sucrose units than those of styrene. Nevertheless, two interesting copolymers were obtained with sucrose monomers bearing hydroxyl groups 1 or with acetylated hydroxyl groups 3, in mole ratios [sug]/[styrene] of 0.49 and 0.64, respectively, corresponding also to the highest sucrose derivative content obtained. Comparing the behaviour of sucrose derivatives, the compounds with a terminal double bond 1 and 3, which were expected to be more reactive, readily gave copolymers with a considerable incorporation of sugar ([sug]/ [styrene] = 0.64), while the crotonoyl sucrose derivatives 2 and 4 were less reactive. In the latter case the highest ratio of incorporation of sugar was [sug]/[styrene] = 0.06. All the copolymers synthesized were amorphous, showing only a glass transition temperature Tg. Copolymers con-

taining pendant sucrose moieties had lower Tg than polystyrene (Tg of polystyrene = 95100 C) indicating a predominant effect of the bulkiness of the side groups which bring free volume to the system. Glass transition temperatures increased exponentially with the mole percent of sugar incorporation for the copolymers with unprotected sucrose monomer (Fig. 2a) and SI). This reversed tendency has been observed previously with different type of sugar monomers [3,7], and could be explained by the restrained movements of the polymer molecules and increased intermolecular forces due to hydrogen bonding between the sucrose moieties. DSC of the sucrose-derived homopolymers did not reveal any glass transition in the range 25225 C. The copolymer samples were also optically active, exhibiting positive optical rotations aD, which increased with the incorporation of sugar monomer in the copolymers (Fig. 2b and SI).

4. Incubation in culture The visual growth rating test is valuable in assessing the performance of polymer during its use under such conditions [32]. The samples were used as the sole carbon source for the fungus, e.g. Aspergillus niger. During incubation with the fungal culture, the spores (black spots) as colonies were observed to grow. Table 9 represents the data for fungal colonization/fungal growth (visual growth) on the surface of polymer lm after 90 days of culture

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Fig. 3. Photograph after 30 days of incubation of sample in a fungal culture and microscope image of the same after 90 days. The fungal growth (P60%) indicates very good partial biodegradability of the 2/styrene sample.

incubation. Initiation of fungal growth could be seen by microscope within 1520 days (the full data of the tests is contained in the SI). The absence of any colonization in a control petri dish (without polymer sample) clearly suggested that fungus was using the polymer specimen as a sole source of carbon. The higher colonization could be attributed to easy consumption of short chains as energy source by fungus with increasing incubation time in culture which concludes that the copolymer was bio-assimilated during microbial attack. The photographs (Fig. 3 and SI) of the cultured sample showed the eroded surface with some residue. The microbial adhesion onto the surface is evident after 30 days of incubation and their subsequent penetration into the polymer was rapid and the polymer consumed. Three different copolymer samples were tested by this procedure: 1/styrene and 2/styrene, bearing sucrose moieties with hydroxyl groups. These samples showed very good partial biodegradability with >60% fungal growth and interestingly, 3/styrene bearing acetylated sucrose moieties was biodegradable with 25% fungal growth (see SI). This lower biodegradability could be caused by the necessity to hydrolyse the acetate esters before the fungus consumes the sugar. Controlled biodegradation is very promising for future applications of this type of polymers. As expected, the copolymers with sucrose moieties showed higher biodegradability than polystyrene alone and resulted in polystyrene enriched residue. After fungal degradation of the sugar fraction the remaining lower molecular weight polystyrene fragments were tested for toxicity. No toxic effects were observed on earthworms living in soil treated with the oligo-styrene fragments. Similarly, sh were not affected by the presence of the fragments in the tank for an extended period. The oligo-styrene fragments mixed in soil were also put in cage containing rats; also no toxic effects were observed. In summary, novel regioisomerically-pure vinyl esters of sucrose were synthesised directly from sucrose in good yields using a simple, mild and selective one-step Mitsunobu procedure. These esters have been copolymerised with styrene by a free radical process, yielding unbranched linear polymer materials with pendant sucrose moieties. Higher incorporation of the sucrose monomer was

achieved using 6-O-methacryloyl sucrose monomer. The characterisation of the polymer products by the average molecular weight, as well as some physical properties enabled an assessment of structural, thermal, mechanical and rheological information. Biodegradation tests on the polymer samples bearing sucrose and acetylated sucrose moieties using a microbial fungal ( A. niger) culture method indicated good partial biodegradability of the samples. Acknowledgment This work has been supported by Fundao para a Cincia e a Tecnologia (PTDC/QUI/72120/2006). Appendix A. Supplementary data Supplementary data associated with this article can be found, in the online version, at doi:10.1016/j.eurpolymj. 2010.02.002. References
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