Synthesis and Characterization of DifferentlySubstituted Phenyl Hepta Isobutyl-PolyhedralOligomeric Silsesquioxane/PolystyreneNanocomposites

Ignazio Blanco, Francesco A. Bottino, Gianluca Cicala, Alberta Latteri, Antonino ReccaDepartment of Industrial Engineering, University of Catania, V.le A. Doria 6, Catania 95125, Italy

Variously substituted polyhedral oligomeric silses-quioxanes (POSSs)/polystyrene (PS) nanocompositesof general formula R7R0(SiO1.5)8/PS (where R 5 isobutyland R05 4-methoxyphenyl, 4-methylphenyl, 3,5-dime-thylphenyl, 4-fluorophenyl, 2,4-difluorophenyl, 4-chloro-phenyl) were prepared by in situ polymerization ofstyrene in the presence of 5% w/w of POSS. Theactual filler concentration in the obtained nanocompo-sites was checked by 1H NMR spectroscopy. Scanningelectron microscopy and FTIR spectroscopy evidencedthe presence of filler-polymer interactions. Inherentviscosity (ginh) determinations indicated that the aver-age molar mass of polymer in halogenated derivativeswas lower than neat PS, and were in agreement withcalorimetric glass transition temperature (Tg) measure-ments. Finally, a comparative study concerning thethermal stability of synthesized nanocomposites wascarried out in both inert (flowing nitrogen) and oxida-tive (static air) atmospheres into a thermobalance, inthe scanning mode, at 10�C min21, and the tempera-tures at 5% mass loss (T5%), of various compoundswere determined. The results were discussed andinterpreted. POLYM. COMPOS., 35:151–157, 2014. VC 2013Society of Plastics Engineers

INTRODUCTION

The synthesis of novel polymeric materials with mani-

fold properties have recently become of great importance

to polymer chemistry and plastic technology. Particularly

in the last decade, there has been growing interest in the

chemical modification of traditional polymers with the

aim of enhancing their chemical and physical properties

and making them useful for special applications. Polymer

composites have shown the ability to balance traditional

polymer properties such as low part weight and easy of

processability with the strength and stiffness of reinforc-

ing agents. Polystyrene (PS) is one of the more produced

thermoplastic polymers due to its versatile application in

different fields. Because of its low cost, good process-

ability, transparency, and good electrical property, PS

products are present almost everywhere. PS can be found

in applications where abrasion, chemical resistance, as

well as thermal stability are required [1] and therefore

lend it to act as a matrix for polymer composites. When

considering the development of composites based on

thermoplastic polymers, and more specifically PS, it is

particularly difficult to ensure good interfacial adhesion

between the matrix and the reinforcing agents. This

shortage of compatibility between many reinforcing

agents and PS is due to its inert nature and the lack of

reactive groups (as compared with thermosetting systems

and, indeed, other engineering thermoplastics), which

limits the level of interaction [2]. Hybrid materials with

superior structural and functional properties can be

obtained by incorporating nanofillers into polymer matri-

ces. Carbon nanotubes, layered silicates, and others [3–9]

are used to prepare organic-inorganic hybrid systems,

but, in the last decade, polyhedral oligomeric silsesquiox-

anes (POSSs) have attracted the attention for the use as

fillers in the production of polymer based nanocompo-

sites [10–15].

The POSS general formula is (R-SiO1.5)n, where n 5 8,

the Si/O ratio is 2/3, whilst the organic R groups, which

can be the same or different, are linked to a silicon-

oxygen cage. A typical POSS nanoparticle (Fig. 1) is thus

formed by an inorganic Si8O12 nanostructured cubic cage,

surrounded by eight organic groups such as alkyl, aryl, or

any of their derivatives, linked to the cage silicon atoms

by covalent bonds. The cubic silica cores are completely

defined as “hard particles” with a 0.53 nm diameter and a

spherical radius of 1–3 nm including peripheral organic

units. If in a hybrid composite, these hard particles are

linked to organic component with known architecture, a

nanocomposite with completely defined interfacial com-

ponent between organic and inorganic phase can be

obtained [16].

Correspondence to: Ignazio Blanco; e-mail: iblanco@dii.unict.it

DOI 10.1002/pc.22644

Published online in Wiley Online Library (wileyonlinelibrary.com).

VC 2013 Society of Plastics Engineers

POLYMER COMPOSITES—2014

Since some years, we are interested in the study of PS

based nanocomposites [17] to obtain products having bet-

ter properties than virgin polymer, in particular higher

thermal stability, which is important because these prod-

ucts can be subjected to high temperatures during proc-

essing or in service. A fine dispersion at molecular level

of a POSS into polymer matrix is requested to obtain the

best exploitation of its properties when used as filler for

nanocomposites. Due to this reason, we focused our atten-

tion on asymmetric R7R0(SiO1.5)8 (where R 5 cyclopentyl

or isobutyl group and R05 unsubstituted or substituted

phenyl group), owing to symmetric R8(SiO1.5)8 leads gen-

erally to auto-aggregation phenomena of POSS molecules

[18,19]. Therefore, the opportune selection of R and R0

groups can allow to obtain products where the chemical-

physical filler–polymer interactions are prevalent on the

POSS-POSS ones. We thus first synthesized and charac-

terized some hetero-substituted POSSs [20,21] and we

then carried out other investigations in order to verify if

and at which filler concentration these molecules give

rise to nanocomposites with better thermal properties than

neat PS [19,22–26].

To have a more complete picture of the properties of

the nanocomposites of our interest, in this work we syn-

thesized and characterized six PS-based nanocomposites

having as fillers all the phenyl hepta isobutyl POSSs

(ph,hib-POSSs) previously studied [21]. All samples were

prepared from reactant mixtures at 5% w/w POSS/PS,

owing to this composition appeared to give rise, accord-

ing to some our preceding experiments [22,25], to nano-

composites showing most enhanced thermal stability than

neat PS. The formulae of various POSSs are reported in

Table 1.

The characterization of PS and obtained nanocompo-

sites was made by 1H NMR spectroscopy to check the

actual filler content and by scanning electron microscopy

(SEM) to verify the filler dispersion at nanometric level.

Differential scanning calorimetry (DSC) was performed

to determine glass transition temperature (Tg) and inherent

viscosity (ginh) measurements were carried out to check if

the presence of various substituted ph,hib-POSSs affected

the average molar mass of PS. Thermogravimetric (TG)

and Differential Thermogravimetric (DTG) analysis, in

both flowing nitrogen and static air atmosphere, were

finally carried out to study the thermal behavior of our

nanocomposites and to determine the temperature at 5%

mass loss (T5%).

EXPERIMENTAL

Materials

Styrene (Aldrich Co.) was purified by passing it

through an inhibitor removal column. 2,2-Azobis(isobu-

tyronitrile), AIBN, (98% Aldrich Co.) was recrystallized

twice from dry ethanol at temperatures less than 40�Cand out of direct light. Toluene was stirred over calcium

hydride for 24 h and distilled in a nitrogen atmosphere.

Tetrahydrofuran (THF) was distilled over a Na–benzophe-

none mixture.

The preparation of variously substituted ph,hib-POSSs

was first carried out. To this aim, isobutyltrimethoxysi-

lane and phenyltrimethoxysilane (Aldrich Co.) were used

as received. 4-Fluorophenyltrimethoxysilane, 4-chlorophe-

nyltrimethoxysilane 2,4-difluorophenyltrimethoxysilane,

4-methylphenyltrimethoxysilane, xyliltrimethoxysilane,

and 4-methoxyphenyltrimethoxysilane were prepared

from the appropriate Grignard reagent and Si(OCH3)4

[27–30]. The isobutyltrisilanol (iC4H9)7ASi7O9 (OH)3

was prepared according to literature methods [31]. Substi-

tuted POSSs were prepared by corner capping reaction of

isobutyltrisilanol with the suitable aryltrimethoxysilane.

The same procedure was used for all compounds and the

details of preparation are reported in Ref. [21].

FIG. 1. Molecular structure of ph,hib-POSS (a) planar view and (b) three-dimensional view. [Color figure

can be viewed in the online issue, which is available at wileyonlinelibrary.com.]

152 POLYMER COMPOSITES—2014 DOI 10.1002/pc

Nanocomposites were then prepared by in situ poly-

merization of 5% w/w POSS/styrene mixtures in toluene.

The details of free-radical polymerization procedure are

described, as an example, for compound 1. Styrene mono-

mer (3.80 g) and 4-methoxyphenyl hib-POSS (0.20 g)

were dissolved in 40 ml of toluene, and AIBN radical ini-

tiator (12 mg) was added; the mixture was frozen in a liq-

uid nitrogen bath, degassed with a vacuum pump, and

then thawed. This operation was repeated three times and

then the tube, sealed under vacuum, was heated at 70�Cfor 24 h under stirring. The clear solution was poured

into a large excess of methanol (600 ml), the precipitated

nanocomposite was collected by filtration and dried under

vacuum at 40�C. The yield was 3.28 g (82%). The same

polymerization procedure was used to prepare neat PS

and compounds 2 (yield 79%), 3 (yield 81%), 4 (yield

79%), 5 (yield 80%), and 6 (yield 83%).

1H NMR Spectroscopy

1H NMR spectra were recorded by a Varian Unity

Inova instrument (1H 500 MHz), using CDCl3 as solvent

and TMS as internal standard.

IR Spectroscopy

Fourier transform infrared (FTIR) spectra were traced

by a Perkin Elmer Spectrum 100 spectrometer, using an

universal ATR sampling accessory. Spectra were recorded

at r.t. from 4000 to 600 cm21 with a resolution of 4.0

cm21, directly on compounds, without any preliminary

treatment.

Viscosity Measurements

An Ubbelohde suspended-level viscosimeter and solu-

tions of polymers in chloroform at the concentration of

1.0 g/dL and at temperature of 25 6 0.1�C were used to

measure inherent viscosities (ginh 5 lngr/C, where

gr 5 relative viscosity, and C 5 polymer concentration).

Scanning Electron Microscopy

All SEM images were obtained by using a field-

emission scanning electron microscope Zeiss FE-SEM

Supra 25 microscope under high vacuum at a voltage of

15.0 kV with a working distance of 6.0 mm.

DSC Measurements

A Mettler DSC 20 differential scanning calorimeter,

coupled with a Mettler TC 10 A processor as control and

evaluation unit, was employed for the determination of

glass transition temperature. The enthalpy and temperature

calibrations of equipment were made according to the pro-

cedure suggested by the manufacturer and reported in our

previous work [32]. Calibrations were repeated every two

weeks. Samples of about 5.0�3 1023 g, held in sealed alu-

minum crucibles, and a heating rate of 10�C min21 were

used for measurements.

TG Analysis

The thermal degradations of the studied compounds were

carried out into a Mettler TA 3000 thermobalance, coupled

with the same Mettler TC 10 A processor as control and

TABLE 1. Molecular structure of the various ph,hib – POSSs used for the synthesis of PS nanocomposites.

1 2 3

4-Methoxyphenyl hib-POSS 4-Methylphenyl hib-POSS 3,5-Dimethylphenyl hib-POSS

4 5 6

4-Fluorophenyl hib-POSS 2,4-Difluorophenyl hib-POSS 4-Chlorophenyl hib-POSS

R5 CH 3ð Þ2CH-CH 2-

DOI 10.1002/pc POLYMER COMPOSITES—2014 153

evaluation unit used for DSC measurements. The tempera-

ture of furnace was calibrated according to the procedure

suggested by Mettler and was repeated every month.

Degradation experiments were carried out in dynamic

heating conditions, from 35 to 700�C, in both flowing

nitrogen (0.02 L min21) and a static air atmosphere, at

the heating rate of 10�C min21. Samples of about 5

3�1023 g, held in alumina open crucibles were used and

their masses were measured as a function of temperature.

These data were later used to plot the percentage of unde-

graded sample (1-D)% as a function of temperature,

where D 5 (Wo 2 W)/Wo, and Wo and W were the masses

at the starting point and during scanning.

RESULTS AND DISCUSSION

The actual POSS contents in the nanocomposites syn-

thesized by in situ polymerization of styrene, starting

from mixtures at 5% w/w POSS/PS, were at first deter-

mined by 1H NMR spectroscopy. The filler percentages

were calculated through the ratio of hydrogen atoms of

POSS and those of PS and all these values were quite in

agreement with each other. The POSS content for each

compound was only slightly different than 5% and was

reported in Table 2.

The FTIR spectra of 1 – 6 compounds were thus car-

ried out and compared with those of neat PS and corre-

sponding POSSs. In all cases the shift of the sharp band

near 1080 cm21, present in the POSSs spectra and attrib-

utable to SiAO bonds [20,21], was observed for all the

nanocomposites, thus indicating the presence of filler-

polymer interactions. Since no substantial differences

were found among various investigated POSS/PS systems,

for the sake of shortness we report here the spectra con-

cerning the compound 2 only (Fig. 2), in which this band

shifts from 1076 cm21 (for the POSS) to 1096 cm21 (for

the nanocomposite). Nanodispersion of filler into polymer

matrix was confirmed by SEM investigations as evi-

denced in Fig. 3 where, despite the presence of some

spheres of diameter ranging from 200 nm to 1 mm due to

the use of toluene as solvent [33], POSS-PS interactions

(for sample 1 and 2 respectively) are shown.

Since it is well known in literature [34] that the ther-

mal stability of polymer is dependent by the polymer

average molar mass, inherent viscosity determinations on

studied compounds were performed and compared with

that of neat PS (Table 2). The identical ginh values found

for PS, methoxy-, methyl-, and dimethyl- ph,hib-POSS/PS

nanocomposites indicated that, the average molar mass of

PS in nanocomposites 1, 2, and 3, was practically the

same than that of neat polymer. Conversely, the inherent

FIG. 2. FTIR spectra of 4-methylphenyl hib-POSS (a), PS (b), and sample 2 (c).

TABLE 2. POSS percentages, inherent viscosity (ginh), glass transition

temperature (Tg), temperature at 5% mass loss (T5%) of PS, and various

nanocomposites in static air atmosphere and in flowing nitrogen.

Air static atmosphere Nitrogen flow

Compounds POSS (%) ginh (dL g21) Tg (�C)a T 5% (�C)a T5% (�C)a

PS 0.14 98 238 285

1 4.7 0.14 97 275 299

2 4.9 0.14 97 273 301

3 5.4 0.14 96 268 295

4 5.1 0.12 94 254 292

5 4.8 0.11 92 245 283

6 5.1 0.12 94 252 296

aDetermined at 10�C min21.

154 POLYMER COMPOSITES—2014 DOI 10.1002/pc

viscosities of fluoro-, chloro-, and, even more, difluoro-

derivatives were quite lower than that of PS, thus suggest-

ing a sharp decrease of their average molar mass and then

that halogenated POSSs affect the polymerization process.

This influence of halogenated derivatives was also con-

firmed by SEM investigations which showed, for these

compounds, a surface with quite extended fractures (Fig.

4) differently from those observed for methoxy-, methyl-,

and dimethyl- ph,hib POSS/PS nanocomposites for which

a homogeneous surface area was present (Fig. 3).

Tg values, calorimetrically determined and reported in

Table 2, showed the same trend just observed for the

inherent viscosity, thus confirming that the variations of

both parameters observed for halogenated derivatives, in

respect to those of PS and methoxy-, methyl-, and

dimethyl- ones, are driven by the same single factor, it

means the average molar mass. It is, in fact, well known

that ginh and Tg values are strongly dependent on average

molar mass [35].

To determine the resistance of nanocomposites to the

thermal degradation the temperature at 5% mass loss

(T5%) of each compound was considered and listed in

Table 2. This thermal parameter was preferred to the

classical initial decomposition temperature (Ti), obtained

by the degradation TG curves as the intersection

between the starting mass line and the maximum gradi-

ent tangent to the curve [36,37], because was independ-

ent by the slope of the descending piece of degradation

TG curve and then, in our opinion, more reliable to

compare the thermal stability of various compounds

each other.

Degradation experiments were first carried out in inert

atmosphere, in dynamic heating conditions, at the heating

rate of 10�C min21, which was selected because it is a

medium scanning rate among those usually employed for

thermal degradations and is the same of that of our calori-

metric Tg determinations. PS and all studied nanocompo-

sites degraded completely in flowing nitrogen as shown

by the TG degradation curves reported in Fig. 5. Even

though the degradation process proceeded up to complete

mass loss for all compounds, the TG curves exhibited

slight differences: PS, dimethyl-, and difluoro nanocom-

posites degraded completely in a single step, whilst all

the other compounds showed a first very sharp degrada-

tion stage, followed by a little second one at low degrada-

tion rate in the last piece of TG curves. A different

behavior was instead observed in oxidative atmosphere

(Fig. 6) where PS and all nanocomposites degraded up to

complete mass loss in a single step.

To explain the increase in the resistance to the thermal

degradation of various nanocomposites in respect to vir-

gin polymer observable from T5% values (Table 2), we

performed the FTIR spectra of the residues of compounds

1–6 at a temperature (410�C) at which the sample mass is

reduced to about the 10% of the initial one.

The FTIR spectra of the residues so obtained were

compared with that of the residue at 370�C (10% about

of initial sample mass) obtained from the degradation

of neat PS and those of corresponding POSSs. The

presence in the FTIR spectra of the nanocomposites

residues, obtained at 410�C, of the band at 697 cm21

and of some weak bands in the 2900–3100 cm21

range, which are present in PS spectrum, as well as of

the band attributable to SiAO bonds, indicates that, at

this percentage of nanocomposite degradation, bothFIG. 4. SEM image of sample 4.

FIG. 3. SEM images of sample 1 (a) and 2 (b).

DOI 10.1002/pc POLYMER COMPOSITES—2014 155

polymer and filler are present at temperatures higher

than that at which the complete decomposition of neat

PS occurs (Figs. 5 and 6), thus confirming the filler-

polymer interactions and so explaining the thermal sta-

bilization of polymer. The FTIR spectra of the residues

at 410�C of compound 2 and the corresponding POSS

are reported as an example in Fig. 7, together with that

at 370�C of PS.

CONCLUSIONS

Finally, some considerations can be drawn from the

data in Table 2: the T5% values obtained for the 4-

methoxyphenyl, 4-methylphenyl, and 3,5-dimethylphenyl

hib-POSS/PS nanocomposites were largely higher (about

35�C) in static air atmosphere and quite higher (about

15�C) in flowing nitrogen than those of neat PS, thus

indicating an enhanced resistance to the thermal degrada-

tion of nanocomposite in respect to virgin polymer; the

introduction of a methoxy-, methyl, or dimethyl group on

the POSS phenyl ring does not lead to any change of the

inherent viscosity of the relative nanocomposites in

respect to that of PS. By contrast, the introduction of hal-

ogen atoms, leads to the decrease of ginh value, which is

larger if two fluorine atoms are introduced. These results

seem indicate that the presence of halogenated POSSs

reduces the PS polymerization degree and appear in

agreement with Tg determinations, owing to it is well

known that glass transition temperature of polymers

increases on increasing average molar mass [38], and

FIG. 6. TG degradation curves at 10�C min21, in static air atmosphere,

of PS and various ph,hib-POSS/PS nanocomposites. [Color figure can be

viewed in the online issue, which is available at wileyonlinelibrary.

com.]

FIG. 7. FTIR spectra of the residues of 4-methylphenyl hib-POSS (a), sample 2 (b), and PS (c) after ther-

mal degradation in flowing nitrogen.

FIG. 5. TG degradation curves at 10�C min21, under nitrogen flow, of

PS and various ph,hib- POSS/PS nanocomposites. [Color figure can be

viewed in the online issue, which is available at wileyonlinelibrary.

com.]

156 POLYMER COMPOSITES—2014 DOI 10.1002/pc

SEM investigations in which, for the halogen derivatives,

was observed a not homogenous surface area. This behavior

was the same of that we found in the past for a similar series

of phenyl substituted POSS/PS nanocomposites in which the

seven organic groups attached to the silicon cage were

cyclopentyl instead of isobutyl [26]; on considering the

results obtained in a previous work regarding the thermal

stability of an unsubstituted ph,hib-POSS/PS nanocomposite

[25], and unlike the results found for the variously substi-

tuted phenyl hepta cyclopentyl-POSS/PS nanocomposites

[26], the introduction of one substituent on the POSS phenyl

group lowers the resistance to the thermal degradation of

obtained nanocomposites, which however is still higher than

that of neat PS, only for filler with electron-withdrawing (as

fluorine and chlorine atoms) character. Conversely the T5%

values obtained for nanocomposites filled with phenyl POSS

methyl- or methoxy-substituted (groups whose electron-

donor character is well known) were practically the same to

those found in the past for the unsubstituted ph,hib-POSS/PS

and the phenyl hepta cyclopentyl-POSS/PS nanocomposites

respectively, thus confirming their higher resistance to the

thermal degradation; the introduction on the POSS phenyl

group of a second substituent, identical to the first one, leads

to a further T5% decrease, in this case independently on its

electron-donor or electron-withdrawing character and up to

values similar than that of polymer matrix; the T5% values

obtained in oxidative atmosphere were lower than those

under nitrogen, but the T5% increments in respect to neat PS

were higher. The enhanced resistance to the thermal degra-

dation of nanocomposites in respect to virgin polymer was

confirmed also in flowing nitrogen but only for methoxy-,

methyl-, and dimethyl-ph,hib-POSS/PS nanocomposites,

while T5% values of fluoro-, difluoro-, and chloro-ph,hib-

POSS/PS ones were quite similar to that of PS.

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