Engineering Journal Preparation and Characterization of Cross-Linked Polymer Supports For Catalysts Immobilization

International Journal of Engineering Research & Science (IJOER)
ISSN: [2395-6992]
[Vol-2, Issue-2, February- 2016]
Preparation and characterization of cross-linked polymer

supports for catalysts immobilization
Maria P. Bracciale1, Alessandra Broggi2*, Elena Bartollini3, Francesca Sbardella4, Matteo
Poldi5, Assunta Marrocchi6*, Maria L. Santarelli7*, Luigi Vaccaro8*
1,2,4,5,7
Dipartimento di Ingegneria Chimica Materiali Ambiente, Universit di Roma La Sapienza, Via Eudossiana 18, 00185
Roma, Italy;
3,6,8
Laboratory of Green Synthetic Organic Chemistry, Dipartimento di Chimica, Universit degli Studi di Perugia, Via Elce
di Sotto 8, 06123 Perugia, Italy.
Abstract A series of macroporous cross-linked polystyrenes for applications as supports in catalysis have been
synthesized and characterized in terms of their structural, thermal and morphological features. In this regards, we have
shown how Fourier-transformed infrared spectroscopy mapping (-FTIR) may represent a very useful and easy-to-handle
tool for the advanced spatial characterization of substituted cross-linked resins at a single bead level, thereby helping
synthetic chemists in the prediction of their behavior during chemical processes. Further, scanning electron microscopy
(SEM), thermal analysis (MTDSC), and N2 absorption (BET) measurements have been performed. Direct correlations
between the polymerization conditions and resins chemical-physical properties have been identified.
Keywords Polymer catalyst supports; Green Chemistry; macroporous resins; polystyrene; micro-FTIR
I.
INTRODUCTION
Catalysis underpins the chemical/petrochemical industry, being fundamental to the chemical production, e.g. fuels, plastics,
etc. Indeed, around 90 percent of chemical manufacturing processes use catalysis to enhance production efficiency and
reduce energy use, thereby reducing, in turn, greenhouse gas emissions. [1] Currently, the general trend in catalysis is the
engineering of heterogeneous systems that should allow the recovery and reuse of the catalyst [2-5], therefore solving the
crucial economic issues as well as environmental concerns. The usually high catalyst cost can be affordable in commercial
applications only when the productivity of the catalyst, measured as total kg of products produced per kg of catalyst, is high
enough to make the chemical process economically viable.
Besides, the principles of Green Chemistry (or Sustainable Chemistry) [6] express the need of industry to make maximum
efforts to minimize waste, particularly if containing toxic/exhaustive metals such as those typically present in transition metal
catalytic systems [7]. In this regard, over the past decades a large number of catalysts have been supported on a variety of
materials ranging from inorganic/organic polymers to mesoporous silica [1-5].
Catalyst supports based on organic insoluble (cross-linked) polymers are arguably among the most versatile supports in the
literature [1-5]. In particular, insoluble polymers supports are advantageous since, for instance, several catalysts immobilized
on the insoluble matrix show enhanced stability to hydrolysis and oxidation, they are easier to handle, and generally give
purer products in chemical processes. Further, the development of highly functional group tolerant controlled and living
polymerization methods [8-14] has allowed for the tuning of the structure and density of catalyst sites along polymers and the
easy incorporation of catalyst into polymer structures. Nevertheless, the use of insoluble polymers presents some drawbacks,
such as lower activities and selectivities when compared with their non-supported analogues. Diffusion effects, accessibility
of the catalytic sites by the reagents in solution, and site heterogeneity might be considered in part responsible for these
results [1-5, 15-16]. In this regards, the availability of analytical tools enabling the determination of functional groups
distribution and accessibility of reagents, which can be of simple and general use, is rather limited.
We have contributed [17-21] to the development of sustainable and efficient procedures based on the use of metal-free
catalysts supported on macroporous cross-linked copolymers of 4-vinylbenzylchloride with divinylbenzene [22]. While often
successful in the recycling as well as the easy separation from the reaction mixtures, the use of such supported catalytic
systems led, in some cases, to the occurrence of slow reactions and poor yields.
The objective of the present paper is to provide an informed picture of the synthesis-structure-morphology correlation in a
wide set of such resins, and, ultimately, to help overcome failures experienced with attempts to use some polymer supports.
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Particularly, herein we show how Fourier transformed infrared micro-spectroscopy (-FTIR) technique [23-24] can become a
very useful tool for the routine analysis of polymer-supported catalysts, to examine functional groups distribution and
accessibility of reagents at a single-bead level. Indeed, most efforts in examining the properties of solid supports focus on
surface area, porosity and swelling of the beads, whereas relatively little attention has been given to the site of
functionalization. Heterogeneous micro-domains within a bead can yield important consequences for the macroscopic
properties (e.g. swelling) [25], and can lead to inhomogeneous reactivity of functional groups within a region of a bead.
To the best of our knowledge, up to now only one relevant report has dealt with the feasibility of using -FTIR to examine
insoluble polymer catalyst supports. Indeed, in 2004, Mandair et al. [24] successfully exploited this technique on flattened
resin beads.
We report for the first time the use of IR reflectance mapping to provide direct evidence for the homogeneity of resin beads
in their original spherical form. No flattening is useful when quantifying species immobilized on highly cross-linked resin
beads since these latter shatter if compressed.
Further, we present the resins characterization by scanning electron microscopy (SEM), and measuring the pore size, surface
area, and thermal decomposition temperature. Trends in the resin surface area and porosity are identified and analyzed.
II.
2.1
RESULTS AND DISCUSSION
Resins preparation.
The synthesis of resins 1a-o was performed by ,-azoisobutyronitrile (AIBN)-initiated suspension copolymerization of
vinylbenzylchloride (2) and divinylbenzene (3) mixture using 2-ethyl-hexanoic acid (2-EHA), 1-chlorodecane (1-CD), and
cyclohexanol (COX) as porogens (or pore-formers) (Scheme 1).
Cl
Porogen
AIBN 1% w/w
85C, 24h
2
Cl
Aqueous phase
1a-o
3
4
SCHEME 1. SYNTHESIS OF PS-Cl RESINS 1a-o

In the case of 1h and 1m, styrene co-monomer was added in low percentage (2% and 4%, respectively) to modulate the
resins chloromethyl content (Scheme 1 and Table 1). The required porogens were selected bearing in mind their effectiveness
[26-31] in generating macroporous structures. Moreover, the choice of three chemically different porogen (acidic, polar
protic, polar aprotic) was made to identify a correlation between support characteristics and the nature of the porogen.
The polymerization yields were generally good (65-78%, Table 1) and in agreement with the expected values. For all the
porogens, when a low concentration (0.1%) of poly(vinyl alcohol) (PVA1) stabilizer (MW 13.000-23.000) was used,
powdered/scaled products were obtained (Table 1).
In the case of 2-EHA porogen, the use of high-molecular weight PVA4 stabilizer (MW 85.000-124.000) gave spherical
beaded products for both stabilizer concentrations (0.1% and 0.4%). When COX and 1-CD porogens were used, a low
concentration of stabilizer (PVA1 or PVA4) always led to powdered or scaled resins. On the other hand, in the case of COX,
spherical beaded products were obtained with high concentration (0.4%) of PVA4 provided that a different VBC/S/DV (4vinylbenzylchloride/styrene/divinylbenzene) co-monomer ratio of 0.6/0/0.4 or 0.6/0.2/0.2 was used (entries 8 and 9, Table 1).
In the case of 1a-b, 1h-n, (i.e. spherical beaded products) typical average bead diameters in the range of 25-100 m were
obtained. Importantly, a narrow size distribution of the beads within each resin was achieved. Indeed, size distribution is
often a critical factor for high quality synthesis supports [32]. The use of cyclohexanol generated the smallest particle
(average size ~100 m).
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TABLE 1
POLYMERS 1a-o FEATURES AND SYNTHESIS CONDITIONa
Entry
Polymer
Stabilizer (%)
Porogen
VBC/S/DV
Yields (%)
Physical format
1
1a
PVA4 (0.1)
2-EHA
0.8/0/0.2
72
beads
2
1b
PVA4 (0.4)
2-EHA
0.8/0/0.2
75
beads
3
1c
PVA1 (0.1)
2-EHA
0.8/0/0.2
68
powder
4
1d
PVA1 (0.4)
2-EHA
0.8/0/0.2
70
powder
5
1e
PVA1 (0.1)
COX
0.8/0/0.2
65
powder
6
1f
PVA4 (0.1)
COX
0.8/0/0.2
70
scales
7
1g
PVA4 (0.4)
COX
0.8/0/0.2
71
powder
8
1h
PVA4 (0.4)
COX
0.6/0.2/0.2
78
beads
9
1i
PVA4 (0.4)
COX
0.6/0/0.4
73
beads
10
1j
PVA1 (0.4)
COX
0.8/0/0.2
65
beads
11
1k
PVA4 (0.1)
1-CD
0.8/0/0.2
71
scales
12
1l
PVA4 (0.4)
1-CD
0.8/0/0.2
68
beads
13
1m
PVA4 (0.4)
1-CD
0.4/0.4/0.2
75
beads
14
1n
PVA1 (0.4)
1-CD
0.8/0/0.2
70
beads
15
1o
PVA1 (0.1)
1-CD
0.8/0/0.2
70
powder
a
PVA1= poly(vinyl alcohol) (MW 13.000-23.000); PVA4= poly(vinyl alcohol) (MW 85.000-124.000); 2-EHA= 2ethylhexanoic acid; COX= cyclohexanol; 1-CD= 1-chlorodecane; VBC/S/DV= 4-vinyl benzyl
chloride/styrene/divinylbenzene
Note here that powders are not preferred in many large-scale applications, owing to dusting problems and excessive pressure
drops across the catalyst in fixed-bed reactors [33]. Further, irregularly shaped (e.g. scaled resins) particles may be
susceptible to mechanical attrition, and breakdown to fines [34]. Therefore resins 1c-g, 1k, 1o were not investigated further
2.2
Resins characterization
The FTIR spectra of resins 1a-b and 1h-n are reported in Figure 1 and Figures SI1-7.
436.22
415.19
553.54
709.64
674.41
638.56
819.26
909.63
1016.29
1265.18
1212.48
1181.94
1143.20
1091.89
1510.98
1485.47
1443.95
1421.20
1359.59
1606.69
1701.80
3018.61
2919.86
0.01
0.02
Absorbance Units
0.03 0.04 0.05
0.06
0.07
3352.26
In all cases, they exhibited a series of strong peaks at 1421cm-1 and 675 cm-1, which were attributed to the characteristic
absorptions of the chloromethyl group CH2Cl. The band at 675 cm1 corresponds to the stretching vibration of CCl bond,
and the band at 1421 cm1 is corresponding to the bending vibration of -CH2 in CH2Cl. Besides, the IR spectra exhibited
two peaks at 1265 cm1and 823 cm1, which were attributed to the vibration absorptions of =CH bond of the CH2Cl psubstituted benzene rings [35].The band at ~3300 cm-1 corresponds to the presence of a low degree of hydroxyl groups
content in the resins. This might be explained by the partial hydrolysis of the chloromethylene groups in vinylbenzene
chlorides. Indeed, suspension polymerizations are carried out at elevated temperatures in the presence of excess water, and it
is not therefore surprising that this side reaction occurs [36-39].
4000
3500
3000
2500
2000
1500
Wavenumber cm-1
1000
500
FIGURE 1. FTIR ANALYSIS OF POLYMER 1a

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To demonstrate the effective distribution of Cl groups on chloromethylated polystyrene resin beads, a -FTIR analysis
(Fourier transformed infrared micro-spectroscopy) [23-24] was performed (see also Experimental Section).
(a)Resin 1a
(d) Resin 1a
(b) Resin 1i
(e) Resin 1i
(c)Resin 1i
(f)Resin 1i
FIGURE 2. SPECTROSCOPIC 2D IMAGES OF THE SPATIAL DISTRIBUTION OFCL GROUPS (A-C). OPTICAL MICROSCOPY
IMAGES 15X (D-F) SHOWING THE HALF-CUT BEAD MAPPING TRACE. ALL SPECTRA WERE COLLECTED IN REFLECTION
1
MODE WITH A 3 cm SPECTRAL RESOLUTION, AND THE IMAGES WERE OBTAINED BY MONITORING THE PEAK CENTRED AT
675 cm1; THE ABSORPTION INTENSITY WAS MEASURED AND EXPRESSED AS ARBITRARY UNITS.
In order to observe the active site spatial distribution, the peak centered at 675 cm1 (i.e. CCl stretching vibration frequency)
was monitored throughout the half-cut resin beads (Figure 2 and SI8). The resulting 2D images (Figures 2a-c and Figures
SI8a-e) indicated that the spatial distribution of -Cl groups is generally regular and homogeneous for samples deriving from
the use of a high concentration (0.4%) of PVA stabilizer (Figures 2b-c and Figures SI8a-e). Further, a better homogeneity in
Cl distribution may be generally observed for samples prepared through the use of high-molecular weight PVA4 compared
to PVA 1stabilizer, as exemplified in Figure 2b (resin 1i) and Figure 2c (resin 1n), respectively.
Next, we also performed nucleophilic substitution of the chlorine atoms in the representative resin 1l by 1,5,7triazabicyclo[4.4.0]dec-5-ene (TBD) base in dioxane at 60C [20]. The -FTIR analysis of the resulting catalytic system
actually demonstrated a regular and homogeneous distribution of TBD active sites. The most obvious evidence of this was
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the disappearance of the chloromethyl band at 675 cm-1 and the appearance of the C-N band at 1370 cm-1 (i.e. C-N stretching
vibration frequency) (Figures SI9-10) on the overall bead surface [17]. These findings anticipated a good site accessibility for
resin 1l, thereby further pointing out the utility of such analytical technique.
The micro analytical data (C, H) obtained from elemental analysis indicated contents of carbon and hydrogen in a range of
72.98-81.07% and 6.42-7.44% respectively, which correspond to a resin chlorine content (loading) in the range 3.09-4.73
mmol/g.
BrunauerEmmettTeller (BET) [32] analyses were performed to determine surface area, average pore volume, average pore
size, and pore size distribution (Table 2 and Figure SI11-18). A direct correlation [31,34] may be observed for resins through
1-chlorodecane porogen (entries 12-14, Table 2). Indeed, when PVA4 is used in the case of polymers 1l and 1m (entries 1213, Table 2), high values of surface area were obtained (107.1 m2/g and 78.3 m2/g, respectively). When PVA1 at the same
concentration (0.4%) is used, polymer 1n (entry 14) resulted in a low value surface area (24.6 m2/g). In the case of
cyclohexanol porogen (entries 8-10, Table 2), when PVA1 is used (resin 1j) the highest average pore size was achieved (107
and 396 , respectively). On the other hand, resins 1i prepared by employing high-molecular weight PVA4, gave lower
average pore radius and average pore volume (entry 9 vs 10, Table 2).
This finding indicated that despite an excellent distribution of Cl groups (Figure 2b), resin 1i may feature a scarce
accessibility of the active sites by solvents/reagents when used as catalyst support, thereby leading to a reduced efficiency of
the catalyst itself.
TABLE 2
SOLID-STATE POROSITY DATA OF POLYMERS 1a-b and 1h-n
Surface area (m2/g)
Average pore volume (cm3/g)
Entry
Polymer
Average pore radius ()
1a
5.0
0.0188
77
1b
27.2
0.29
85
1h
3.4
0.02
107
-3
1i
0.3
10
10
1j
23.0
0.21
396
12
1l
107.1
0.31
116
13
1m
78.3
0.54
137
14
1n
24.6
0.11
91
In the case of resins prepared with 2-EHA as porogen (entries 1 and 2, Table 1), low surface area (5.0 m2/g and 27.2 m2/g,
respectively) and average pore radius (77 and 85 , respectively) were observed. 1-CD and COX revealed to be the best
porogens in terms of average pore size and surface area, respectively, thereby suggesting the easiest accessibility to
functional Cl groups. Indeed, porogen effects on pore structure and surface area are well-known [40-41]. A rather large
population of mesopores (1.6-33.3 nm) has been generally observed (Figures SI11-18), except for 1i, thereby indicating that
all the porogens are thermodinamically compatible with the polymer matrix and/or the cross-linker percentage [32]. The
smaller types of pore are essential to a high surface area [32].
The resins 1a-b and 1h-n were subjected to modulated temperature differential scanning calorimetry (MTDSC) analysis,
showing high thermal stability in the range of 30-250C (Figure 3 and Figures SI19-25). Particularly, MTDSC plot for 1n
reveals a rearrangement of the crystalline structure for this latter (so-called secondary transitions) occurring at ~220C
(Figure 3).
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Sample: MA50_25 mesh
Size: 8.2000 mg
Method: metodo vaccaro
ISSN: [2395-6992]
File: C:...\polimeri matteo\MA50_25 mesh.001

Operator: TA GF
Run Date: 24-Jan-2013 13:04
Instrument: 2920 MDSC V2.6A
DSC
0.32
0.22
0.11
0.28
0.10
0.18
0.09
0.26
Rev Heat Flow (W/g)
0.20
Nonrev Heat Flow (W/g)
Heat Flow (W/g)
0.30
0.16
0.08
0.24
50
100
150
200
250
Temperature (C)
Exo Down
0.14
300
Universal V4.7A TA Instruments
FIGURE 3. MTDSC ANALYSIS OF POLYMER 1n

Scanning electron microscopy (SEM) was used to investigate polymers surface morphology and particle size (Figures SI2627). Resins 1a, 1h, 1m and 1n (Figures SI26a, SI26c, SI27c and SI27d, respectively) reveal a clear macropores population
even at the bead surface. Resins 1b, 1j and 1l (Figures SI26b, SI27a and SI27b, respectively) showed rough contaminated
surfaces with fragments associated with them or cracks. The contamination is however superficial, as the high-magnification
SEM images of these resins show access to a discrete macroporous structure (Figures SI26f, SI27e and SI27f). Resin 1i
(Figure SI26d), however, shows a fine surface texture, which is rather uniform. SEM images of polymer fracture sections
clearly show in all cases the formation of a typical macroporous structure (Figures SI26e-h and SI27e-h).
III.
3.1
EXPERIMENTAL SECTION
General.
All the commercially available chemicals were purchased at SigmaAldrich and used without any further purification, unless
otherwise noted. 4-vinylbenzylchloride (2), divinylbenzene (3) (80% grade) and styrene (4) (Scheme 1) were extracted three
times with a 5% w/w NaOH solution to remove the polymerization inhibitor (tert-butyl catechol). , Azoisobutyronitrile (AIBN) was re-crystallized from methanol. Suspension polymerizations were run using a three-neck
cylinder-shaped glass vessel, equipped with a mechanical stirrer, condenser, and nitrogen inlet [17]. Elemental microanalyses
were performed using a Fisons EA1106 CHN analyzer using atropine, 2,5-bis-2-(5-tert-butylbenzoxazolyl) thiophene
(BBOT) and phenanthrene as reference standard, with an accuracy of ca. 2 mol/g.
Conventional FTIR spectra were recorded on a VERTEX 70 Bruker Optics instrument, spectral range 4000400 cm-1,
resolution 4 cm-1, equipped with single reflection diamond ATR cell.
-FTIR imaging was performed using a FT-IR microspectrometer Hyperion 2000 (Bruker Optics GmbH) equipped with a
liquid nitrogen cooled MCT detector, in order to get the better signal to noise ratio. The microscope is equipped with a
standard 15x objective. For -FTIR imaging, spectra were collected, in reflection mode, in the mid-infrared (MIR) range of
6004000 cm-1 at a resolution of 3 cm-1 with 128 co-added scans. Sample step was 50 nm. All the data collection and
processing were performed using OPUS 7.0 (Bruker). The measurements were carried out on half-cut resin beads after
embedding in an acrylic resin support (TECHNOVIT 4004, Kulzer), and polishing with conventional methods using silicon
carbide papers with grit 600, 1200 to 2500 (Buehler). The final polishing was attained using a polishing cloth.
BrunauerEmmettTeller (BET) analyses were performed by using an Autosorb iQ-MP/MPXR instrument (Quantachrome).
Modulated temperature differential scanning calorimetry analysis (MTDSC) were performed with a TA instruments 2920
calorimeter with modulated cell cooled by nitrogen flow. Samples were analyzed in opened capsules with heating rate of 10
C/min, 0.5 C modulation and 60s period.
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Scanning electron microscopy (SEM) analyses were performed using an Auriga Zeiss HR FESEM instrument. SEM imaging
of the surfaces of resin samples was performed with accelerating voltages between 5 keV and 30 keV, achieving
magnifications ranging from 100x to 200kx.
3.2
Typical procedure for the preparation of chloromethylated resins PS-Cl 1.
The procedure for the synthesis of chloromethylated resin 1a is reported as an example. Details on the reaction conditions for
the remaining investigated PS-Cl 1 are reported in the Supporting Information.
PS-Cl 1a. A reaction vessel immersed in an oil bath, equipped with condenser, mechanical stirrer and nitrogen inlet/outlet
was charged with water (80 mL), poly(vinyl alcohol) (MW 85,000124,000, 99% hydrolyzed) (0.1%), and NaCl (2.65 g) and
stirred for 24 h at room temperature. A mixture of 4-vinylbenzylchloride (2), (1.6 mL), divinylbenzene (3) (0.4 mL), 2ethylhexanoic acid (2-EHA, 2 mL) and AIBN (0.02 g, 1% w/w monomers) was then added into the reactor. The system was
kept under stirring and purged with nitrogen for 30 min. Then, the reaction was warmed up to 85 C under mechanical
stirring. After 24 h, the reaction was allowed to reach room temperature and the polymer beads were filtered. The product
was washed in a Soxhlet extractor for 24 h with water, THF and hexanes and vacuum dried overnight (yield 72%).
IV.
CONCLUSION
To sum up, a new series of uniformly functionalized macroporous cross-linked resins to be employed as heterogeneous
catalyst supports have been synthesized and characterized in terms of structure, thermal properties, and morphology. In order
to obtain spherical-beaded products, in the case of 2-ethylhexanoic acid (2-EHA) porogen the use of high-molecular weight
stabilizer is required, independently from its concentration. On the other hand, it was found that when cyclohexanol (COX)
or 1-chlorodecane (1-CD) porogens are used, the presence of higher PVA concentration is needed, regardless of the stabilizer
molecular weight. The relative ratio of all components, i.e. co-monomers, porogen, and stabilizer, allowed broad variation in
the (micro) structure of the materials.
We showed for the first time that Fourier transformed infrared micro-spectroscopy (-FTIR) technique can be a powerful
tool for the simple analysis of polymer supports as well as the corresponding immobilized catalytic systems, to examine
functional groups distribution and accessibility of reagents at a single-bead level. This is of particular interest since it helps in
the prediction of resin reactivity and behavior during solid phase synthesis.
Further, we found that the investigated resins feature high average pore size (except 1i), thereby supporting an easy
accessibility to functional Cl groups.
ACKNOWLEDGEMENTS
This research has been developed and partially financed within the National project BIT3G Italian Green Chemistry
Cluster.
We gratefully acknowledge the Universit degli Studi di Perugia, and the Ministero dellIstruzione, dellUniversit e della
Ricerca (MIUR) for the financial support within the program Firb-Futuro in Ricerca ref. N. RBFR08JKHI. Furthermore,
the author thanks Dr. Francesco Mura, Sapienza Nanoscience & Nanotechnology Laboratories (CNIS-SSN-Lab), for his
helpful assistance in SEM analyses.
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processes. J. Catal. vol. 285, pp.216-22, 2012.
[21] S. Bonollo, L.Lanari, J.M.Longo, and L. Vaccaro, E-factor minimized protocols for the polystyryl-BEMP catalyzed conjugate
additions of various nucleophiles to a,b-unsaturated carbonyl compounds. Green Chem. vol. 14, pp. 164-69, 2012.
[22] R.B. Merrifield, Solid Phase Peptide Synthesis. I. The Synthesis of a Tetrapeptide. J. Am. Chem.Soc. vol. 85, pp. 2149-52, 1963.
[23] E.Zanni, G.De Bellis, M.P. Bracciale, A. Broggi, M.L.Santarelli, , M.S., Sarto, C.Palleschi, , and D.Uccelletti, Graphite
Nanoplatelets and Caenorhabditis elegans: Insights from an in Vivo Model. Nano Letters vol. 12, pp. 2740-44, 2012.
[24] G.S. Mandair, Z. Yu, N. Galaffu, M. Bradley, and A.E. Russell, Microscopic infrared mapping of chloromethylated polystyrene resin
beads. Appl. Spectroscopy vol 58, pp. 1282-87, 2004.
[25] K.J.Shea, and G.T. Stoddard, Chemoselective Targeting of Fluorescence Probes in Polymer Networks. Detection of Heterogeneous
Domains in S tyrene-Divinylbenzene Copolymers. Macromolecules vol. 24, pp. 1207-09, 1991.
[26] Q.Liu, Y.Li, S.Shen, and Z.Shanshan, The influence of crosslinking density on the pore morphology of copolymer beads prepared
with a novel pore-forming agent. Mater. Chem. and Phys. vol. 125, pp. 315-18, 2011.
[27] X.Huanga, N. Qiu, D.Yuan, and B. Huang,. A novel stir bar sorptive extraction coating based on monolithic material for apolar,
polar organic compounds and heavy metal ions. Talanta vol. 78, pp.101-06, 2009.
[28] Q.Liu, L.Wang, A. Xiao, H.Yu, Q.Tan, J.Ding, and G. Ren, Unexpected behavior of 1-chlorodecane as a novel porogen in
preparation of high porosity poly(divinylbenzene) microspheres. J. Phys. Chem. C vol. 112, pp.13171-74, 2008.
[29] Q.Q. Liu, L.Wang, A.G. Xiao, H.J. Yu, and Q.H. Tan, A hyper-cross-linked polystyrene with nano-pore structure. Eur. Polym. J.
vol. 44, pp.2516-22, 2008.
[30] A.K. Nyhus, S.Hagen, and A.Bergej, Friedelcrafts reactions of pendant vinyl groups in macroporous monosized poly(metadivinylbenzene) and poly(para-divinylbenzene) particles. J. Polym. Sci. Polym. Chem. vol. 38 pp.1366-78, 2000.
[31] O. Okay, Macroporous copolymer networks. Progress Polym. Sci. vol. 25 pp.711-79,2000.
[32] F.S. Macintyre, and D.C. Sherrington, Control of Porous Morphology in Suspension Polymerized Poly(divinylbenzene) Resins
Using Oligomeric Porogens. Macromolecules vol. 37, pp. 7628-36, 2004.
[33] M.L.Wang, C.H.Wang, and W. Wang, Porous macrobeads composed of metal oxide nanocrystallites and with percolated porosity.
J. Mater. Chem. vol. 17, pp. 2133- 38, 2007.
[34] D.C. Sherrington, Preparation, structure and morphology of polymer supports. Chemical Commun. pp. 2275-86, 1998.
[35] L.Chunling, G.Baojiao, L.Qing, Q. Changsheng, Preparation of two kinds of chloromethylated polystyrene particle using 1,4-bis
(chloromethoxy) butane as chloromethylation reagent. Colloid Polym. Sci. vol. 286, pp.553-61, 2008.
[36] U.Wijaya, Synthesis of Mesoporous Carbons Derived from Hypercrosslinking of Divinylbenzene 4-Vinylbenzyl Chloride Resin.
IPTEK J. Technol. Sci. vol. 18, pp.130-362007.
[37] N.Fontanals, J.Corts, M.Gali, M.R. Merc, P.A.G Cormack, F. Borrull, D.C. Sherrington, Synthesis of Davankov-Type
Hypercrosslinked Resins Using Different Isomer Compositions of Vinylbenzyl Chloride Monomer, and Application in the SolidPhase Extraction of Polar Compounds. J. Polym.Sci. Polym. Chem. vol. 43, pp. 1718-28. 2005.
[38] S.Subramonian, Anion-exchange resins from vinylbenzyl choride: control of hydrolysis during polymerization. React. Funct.
Polym. vol. 29, pp. 129-33, 1996.
[39] R.V. Law, D.C. Sherrington, C.E. Snape, I.Ando, H. Kurosu, Solid-State 13C MAS NMR Studies of Hyper-Cross-Linked
Polystyrene Resins. Macromolecules. vol. 29, pp. 6284-93,1996.
[40] M.H.Mohamed, and L.D. Wilson, Porous Copolymer Resins: Tuning Pore Structure and Surface Area with Non Reactive
Porogens. Nanomater. vol. 2, pp.163-86, 2012.
[41] D.X. Hao, F. L.Gong, W.Wei, G.H. Hu, G.H.Ma, and Z.G. Su, Porogen effects in synthesis of uniform micrometer-sized
poly(divinylbenzene) microspheres with high surface areas. J. Colloid Interf. Sci. vol. 323, pp. 52-59, 2008.
Page | 173
ISSN: [2395-6992]
Supporting information for
Preparation and characterization of cross-linked polymer

supports for catalysts immobilization
Maria P. Bracciale1, Alessandra Broggi2*, Elena Bartollini3, Francesca Sbardella4, Matteo
Poldi5, Assunta Marrocchi6*, Maria L. Santarelli7*, Luigi Vaccaro8*
1,2,4,5,7
Dipartimento di Ingegneria Chimica Materiali Ambiente, Universit di Roma La Sapienza, Via Eudossiana 18, 00185
Roma, Italy; 3,6,8Laboratory of Green Synthetic Organic Chemistry, Dipartimento di Chimica, Universit degli Studi di
Perugia, Via Elce di Sotto 8, 06123 Perugia, Italy.
e-mail: alessandra.broggi@uniroma1.it; assunta.marrocchi@unipg.it; marialaura.santarelli@uniroma1.it;
luigi.vaccaro@unipg.it
General procedure for the preparation of chloromethylated resins PS-Cl 1b-o

PS-Cl 1b. Prepared by following the procedure described in the Experimental Section, Main Text, for 1a. Stabilizer:
poly(vinyl alcohol) (MW 85,000124,000, 99% hydrolyzed) (0.4%) (yield 75%).
PS-Cl 1c. Prepared by following the procedure described in the Experimental Section, Main Text, for 1a. Stabilizer:
poly(vinyl alcohol) (MW 13,000-23,000, 99% hydrolyzed) (0.1%) (yield 68%).
PS-Cl 1d. Prepared by following the procedure described in the Experimental Section, Main Text, for 1a. Stabilizer:
poly(vinyl alcohol) (MW 13,000-23,000, 99% hydrolyzed) (0.4%) (yield 70%).
PS-Cl 1e . Prepared by following the procedure described in the Experimental Section, Main Text, for 1a. Porogen:
cyclohexanol (COX); Stabilizer: poly(vinyl alcohol) (MW 13,000-23,000, 99% hydrolyzed) (0.1%) (yield 65%).
PS-Cl 1f. Prepared by following the procedure described in the Experimental Section, Main Text, for 1a. Porogen:
cyclohexanol (COX); Stabilizer: poly(vinyl alcohol) (MW 85,000124,000, 99% hydrolyzed) (0.1%) (yield 70%).
PS-Cl 1g. Prepared by following the procedure described in the Experimental Section, Main Text, for 1a. Porogen:
cyclohexanol (COX); Stabilizer: poly(vinyl alcohol) (MW 85,000124,000, 99% hydrolyzed) (0.4%) (yield 71%).
PS-Cl 1h. Prepared by following the procedure described in the Experimental Section, Main Text, for 1a. Porogen:
cyclohexanol (COX); Stabilizer: poly(vinyl alcohol) (MW 85,000124,000, 99% hydrolyzed) (0.4%); VBC/S/DV:
0.6/0.2/0.2 (yield 68%).
PS-Cl 1i. Prepared by following the procedure described in the Experimental Section, Main Text, for 1a. Porogen:
cyclohexanol (COX); Stabilizer: poly(vinyl alcohol) (MW 85,000124,000, 99% hydrolyzed) (0.4%); VBC/S/DV: 0.6/0 /0.4
(yield 73%).
PS-Cl 1j. Prepared by following the procedure described in the Experimental Section, Main Text, for 1a. Porogen:
cyclohexanol (COX); Stabilizer: poly(vinyl alcohol) (MW 13,000-23,000, 99% hydrolyzed) (0.4%) (yield 65%).
PS-Cl 1k. Prepared by following the procedure described in the Experimental Section, Main Text, for 1a. Porogen: 1chlorodecane (1-CD); Stabilizer: poly(vinyl alcohol) (MW 85,000124,000, 99% hydrolyzed) (0.1%) (yield 71%).
PS-Cl 1l. Prepared by following the procedure described in the Experimental Section, Main Text, for 1a. Porogen: 1chlorodecane (1-CD); Stabilizer: poly(vinyl alcohol) (MW 85,000124,000, 99% hydrolyzed) (0.4%) (yield 68%).
PS-Cl 1m. Prepared by following the procedure described in the Experimental Section, Main Text, for 1a. Porogen: 1Page | 174
ISSN: [2395-6992]
chlorodecane (1-CD); Stabilizer: poly(vinyl alcohol) (MW 85,000124,000, 99% hydrolyzed) (0.4%); VBC/S/DV:
0.4/0.4/0.2 (yield 75%).
PS-Cl 1n. Prepared by following the procedure described in the Experimental Section, Main Text, for 1a. Porogen: 1chlorodecane (1-CD); Stabilizer: poly(vinyl alcohol) (MW 13,000-23,000, 99% hydrolyzed) (0.4%) (yield 70%).
PS-Cl 1o. Prepared by following the procedure described in the Experimental Section, Main Text, for 1a. Porogen: 1-
540.44
475.62
446.72
416.99
708.18
672.33
637.89
815.36
907.98
1015.60
1088.09
1264.80
1211.44
1442.59
1420.52
1359.00
1510.76
1605.77
1692.83
3015.40
2914.86
0.010
Absorbance Units
0.020
0.030
0.040
3327.45
chlorodecane (1-CD); Stabilizer: poly(vinyl alcohol) (MW 13,000-23,000, 99% hydrolyzed) (0.1%) (yield 70%).
4000
3500
3000
2500
2000
1500
Wavenumber cm-1
C:\Documents and Settings\Bruker\Desktop\misure FTIR\Polimeri luigi - fine 2012\MA57-PsCl.0
1000
Rigaglia Davide
500
rigaglia davide
11/12/2012
FIGURE SI1. FTIR ANALYSIS OF POLYMER 1b.
409.20
540.17
747.15
700.00
672.07
819.60
907.47
1017.20
1088.91
1264.40
1510.63
1492.68
1442.67
1420.67
1602.61
2322.84
3024.06
2918.89
0.005
Absorbance Units
0.010
0.015
0.020
3330.68
Page 1/1
4000
3500
3000
2500
2000
1500
Wavenumber cm-1
C:\Documents and Settings\Bruker\Desktop\misure FTIR\Polimeri luigi - fine 2012\SZ18_35mesh_2.0
1000
Vetrino ATR karen
FIGURE SI2. FTIR ANALYSIS OF POLYMER 1h.
500
P-ATR V70
11/12/2012
Page 1/1
Page | 175
424.51
404.65
549.83
824.37
798.80
745.07
709.47
673.00
638.20
905.57
1018.00
989.70
1095.09
1510.21
1485.78
1442.93
1420.60
1357.66
1312.59
1264.64
1213.02
1182.65
1629.19
1604.55
1701.12
2323.17
ISSN: [2395-6992]
0.01
0.02
Absorbance Units
0.03
0.04
0.05
0.06
3020.29
2920.87
2850.63
4000
3500
3000
2500
2000
1500
Wavenumber cm-1
SI3. FTIR
1000
1i.
C:\Documents and Settings\Bruker\Desktop\misure

FTIR\Polimeri luigi - fine
2012\F46_25mesh.0
Vetrino ATR karen
IGURE
ANALYSIS
OF POLYMER
500
P-ATR V70
11/12/2012
Absorbance Units
0.010 0.015 0.020 0.025 0.030 0.035 0.040
4000
3500
3000
2500
2000
1500
Wavenumber cm-1
SI4. FTIR
1000
1j.

2012\MA52-PsCl.0
Rigaglia Davide
IGURE
ANALYSIS
OF POLYMER
rigaglia davide
708.97
675.14
668.68
638.73
540.83
467.46
437.86
405.48
815.77
908.93
1037.99
1014.77
1264.55
1211.56
1510.41
1485.39
1442.72
1420.60
1362.58
1606.67
1701.45
2356.64
2344.62
2325.43
3015.74
2916.64
2853.76
3331.91
Page 1/1
500
11/12/2012
Page 1/1
Page | 176
411.15
475.21
549.21
708.81
672.45
638.15
820.01
911.50
1017.22
1142.87
1092.75
1318.66
1264.83
1212.93
1442.79
1420.82
1510.58
1610.40
1703.61
2362.52
2342.97
2324.58
3021.94
2918.81
ISSN: [2395-6992]
0.005
Absorbance Units
0.010
0.015
0.020
3313.51
4000
3500
3000
2500
2000
1500
Wavenumber cm-1
1000
500
Rigaglia Davide
rigaglia davide
FIGURE SI5. FTIR ANALYSIS
OF POLYMER
1l.
C:\DOCUMENTS AND SETTINGS\ADMINISTRATOR\DESKTOP\MA53.0
11/12/2012
541.95
699.51
674.88
759.87
823.34
909.06
1017.94
1143.08
1094.35
1264.66
1327.98
1510.73
1492.57
1445.38
1421.30
1602.63
3024.76
2919.40
0.02
Absorbance Units
0.04
0.06
0.08
0.10
3325.67
Page 1/1
4000
3500
3000
2500
2000
1500
Wavenumber cm-1
C:\Documents and Settings\Bruker\Desktop\misure FTIR\Polimeri luigi - fine 2012\SZ12_45mesh.0
1000
Vetrino ATR karen

FIGURE SI6. FTIR ANALYSIS OF POLYMER
1m.
500
P-ATR V70
11/12/2012
Page 1/1
Page | 177
427.20
415.91
554.58
744.41
708.61
672.30
638.23
822.71
911.14
1017.91
1111.42
1264.82
1212.99
1182.96
1510.74
1485.67
1443.18
1421.11
1610.92
2323.52
3021.96
2921.50
ISSN: [2395-6992]
0.01
Absorbance Units
0.02
0.03
0.04
3362.01
4000
3500
3000
2500
2000
1500
Wavenumber cm-1
SI7. FTIR
1000
1o.

2012\MA50_25mesh.0
Vetrino ATR karen
IGURE
ANALYSIS
OF POLYMER
500
P-ATR V70
11/12/2012
Page 1/1
Page | 178
ISSN: [2395-6992]
(a) Resin 1b
(f) Resin 1b
(b) Resin 1h
(g) Resin 1h
(c) Resin 1j
(h) Resin 1j
(d) Resin 1l
(i) Resin 1l
(e) Resin 1m
(j) Resin 1m
FIGURE SI8. SPECTROSCOPIC 2D IMAGES OF THE SPATIAL DISTRIBUTION OFCl GROUPS (A-E). OPTICAL MICROSCOPY
IMAGES 15X (F-J) SHOWING THE HALF-CUT BEAD MAPPING TRACE.
Page | 179
462.33
420.54
406.38
551.50
1509.46
1486.22
1443.85
1442.54
1420.76
1420.36
1369.93
1359.64
1314.16
1302.95
1264.34
1205.74
1182.23
1111.66
1087.15
1049.22
1016.69
908.25
882.65
819.47
807.79
752.37
708.49
672.95
633.25
1609.26
1595.44
2167.10
2162.70
2112.96
2050.54
2050.33
2015.32
1980.84
1980.61
1915.86
1905.35
1790.42
1698.74
2354.52
2323.84
3009.76
2918.05
2916.14
2854.55
3211.31
ISSN: [2395-6992]
0.03
0.04
0.05
0.06
0.07
0.08
0.09
3354.67
4000
3500
3000
2500
2000
1500
1000
500
Wavenumber cm-1
C:\Documents and Settings\Bruker\Desktop\misure FTIR\Polimeri luigi - fine 2012\MA58-PsTBD.0
MA58
Instrument type and / or accessory
16/04/2013
MA41_2
Instrument type and / or accessory
17/04/2013
FIGURE SI9. FTIR ANALYSIS OF POLYMER 1l (BLU LINE) AND 1l AFTER NUCLEOPHILIC SUBSTITUTION OF THE CHLORINE
C:\Documents and Settings\Bruker\Desktop\misure FTIR\Polimeri luigi - fine 2012\MA41-PsCl.0
y-axis [m]
1500
ATOMS BY 1,5,7-TRIAZABICYCLO[4.4.0]DEC-5-ENE (TBD) (RED LINE).

Page 1/1
0.45
500
1000
0.42
0.4
0.38
0.36
0.34
0.32
0.3
0.28
0.26
0.24
0.22
0.2
0.18
0.16
1397-1366
500
1000
1500
x-axis [m]
(a)
0.12
0.1
0.08
0.06
0.04
0.02
0
(b)
FIGURE SI10. SPECTROSCOPIC 2D IMAGE OF THE SPATIAL DISTRIBUTION OF TBD GROUP (A). OPTICAL MICROSCOPY
IMAGE 15X (B) SHOWING THE HALF-CUT BEAD MAPPING TRACE.
Page | 180
ISSN: [2395-6992]
FIGURE SI11. PORE SIZE DISTRIBUTION OF POLYMER 1a.
FIGURE SI12. PORE SIZE DISTRIBUTION OF POLYMER 1b.
Page | 181
ISSN: [2395-6992]
FIGURE SI13. PORE SIZE DISTRIBUTION OF POLYMER 1h.
FIGURE SI14. PORE SIZE DISTRIBUTION OF POLYMER 1i.
Page | 182
ISSN: [2395-6992]
FIGURE SI15. PORE SIZE DISTRIBUTION OF POLYMER 1j.
FIGURE SI16. PORE SIZE DISTRIBUTION OF POLYMER 1l.
Page | 183
ISSN: [2395-6992]
FIGURE SI17. PORE SIZE DISTRIBUTION OF POLYMER 1m.
FIGURE SI18. PORE SIZE DISTRIBUTION OF POLYMER 1n.
Page | 184
G185_45
mesh
InternationalSample:
Journal
of Engineering
Research & Science (IJOER)
Size: 4.2000 mg
File: E:...\polimeri matteo\G185_45

mesh.001
ISSN: [2395-6992]
[Vol-2, Issue-2,
February- 2016]
DSC
Operator: TA GF
Run Date: 24-Jan-2013 16:42
0.50
0.20
0.29
0.47
0.19
0.28
0.44
0.27
0.18
0.26
0.17
0.38
0.35
0.32
0.25
0.24
0.16
0.23
0.15
0.22
0.21
0.14
Rev Heat Flow (W/g)
Heat Flow (W/g)
0.41
0.20
0.29
0.13
0.19
0.26
0.18
0.12
0.17
0.23
0.11
0.16
0.20
50
100
150
200
0.10
300
250
Temperature (C)
Exo Down
Sample: G185_45 mesh

Size: 4.2000 mg
File: C:...\polimeri matteo\G185_45 mesh.001
FIGURE SI19. MTDSC

ANALYSIS OF POLYMER
Operator: TA1a.
GF
DSC
Run Date: 24-Jan-2013 16:04

0.3937
0.2937
0.1937
0.3875
0.2875
0.1875
0.3812
0.2812
0.1812
0.3750
0.2750
0.1750
0.3687
0.2687
0.1687
0.2625
0.1625
0.2562
0.1562
0.2500
0.1500
0.2437
0.1437
0.2375
0.1375
0.3312
0.2312
0.1312
0.3250
0.2250
0.1250
0.3188
0.2187
0.1188
0.3125
0.2125
0.1125
0.3062
0.2062
0.1062
0.3625
0.3562
0.3500
0.3437
0.3375
0.3000
50
Exo Down
100
150
200
Temperature (C)
250
Rev Heat Flow (W/g)
0.2000
Heat Flow (W/g)
0.4000
0.1000
300
FIGURE SI20. MTDSC ANALYSIS OF POLYMER 1b.
Page | 185
Sample:
SZ18_230714
International
Journal
of Engineering Research & Science (IJOER)
DSC
Size: 11.8000 mg
File: E:...\DSC nuovi\230714\SZ18_230714.001

ISSN: [2395-6992]
Operator: mls
Run Date: 23-Jun-2014 14:51
0.30
0.29
0.091
0.24
0.28
0.087
0.22
0.27
Heat Flow (W/g)
0.25
0.24
0.23
0.22
0.079
0.20
0.075
0.18
0.071
0.067
Rev Heat Flow (W/g)
0.083
0.26
0.16
0.21
0.063
0.20
0.14
0.059
0.19
0.18
80
100
120
140
160
180
200
Temperature (C)
Exo Down
0.12
240
220
FIGURE SI21. MTDSC ANALYSIS OF POLYMER 1h.

Sample: F46_230714
Size: 8.0000 mg
File: E:...\DSC nuovi\230714\F46_230714.001

Operator: mls
Run Date: 23-Jun-2014 10:13
DSC
0.40
0.120
0.38
0.115
0.36
0.34
0.110
0.32
0.28
0.26
0.24
0.22
0.20
0.18
0.16
0.105
0.100
0.095
Rev Heat Flow (W/g)
Heat Flow (W/g)
0.30
0.14
0.090
0.16
0.14
0.085
0.12
0.10
80
Exo Down
100
120
140
160
180
200
Temperature (C)
220
0.080
240
FIGURE SI22. MTDSC ANALYSIS OF POLYMER 1i.
Page | 186

Sample: MA52
Size: 6.9000 mg
ISSN: [2395-6992]
DSC
File: C:...\Utente FSC\Desktop\MA52.001

Operator: TA GF
Run Date: 20-Feb-2013 15:02
0.40
0.30
0.28
0.25
0.36
0.27
0.32
0.28
0.19
0.24
0.16
0.13
0.21
Rev Heat Flow (W/g)
Heat Flow (W/g)
0.22
0.10
0.07
0.24
0.18
0.04
0.20
0
50
100
150
200
Temperature (C)
Exo Down
Sample: MA49
Size: 2.6000 mg
0.15
300
250
File: E:\MA53.001
Operator: TA GF
DSC
FIGURE SI23. MTDSC ANALYSIS OF POLYMER
Run Date:1j.
20-Feb-2013 12:41
0.60
0.50
0.38
0.45
0.55
0.34
0.40
0.50
0.45
0.40
0.35
0.30
0.26
0.25
0.22
0.20
Rev Heat Flow (W/g)
Heat Flow (W/g)
0.35
0.30
0.15
0.18
0.30
0.10
0.14
0.25
0.05
0.20
0
Exo Down
50
100
150
200
Temperature (C)
250
0.00
300
FIGURE SI24. MTDSC ANALYSIS OF POLYMER 1l.
Page | 187

Sample: SZ12_230714
Size: 9.2000 mg
ISSN: [2395-6992]
File: E:...\DSC nuovi\230714\SZ12_230714.001

Operator: mls
Run Date: 23-Jun-2014 13:08
DSC
0.40
0.146
0.140
0.134
0.30
0.128
0.122
0.21
0.116
0.110
0.16
0.104
Rev Heat Flow (W/g)
0.35
Heat Flow (W/g)
0.26
0.098
0.25
0.11
0.092
0.086
0.20
140
160
180
200
Temperature (C)
Exo Down
0.06
240
220
FIGURE SI25. MTDSC ANALYSIS OF POLYMER 1m.
(a) Resin 1a
(b) Resin 1b
(c) Resin 1h
(d) Resin 1i
(e) Resin 1a
(f) Resin 1b
(g) Resin 1h
(h) Resin 1i
FIGURE SI26. SCANNING ELECTRON MICROSCOPY IMAGES OF RESINS BEADS PREPARED BY USING (A,B) 2-EHA
POROGEN, (C,D) COX POROGEN, AND THE CORRESPONDING MACROPOROUS RESIN FRACTURES (E-H).
Page | 188
ISSN: [2395-6992]
(a) Resin 1j
(b) Resin 1l
(c) Resin 1m
(d) Resin 1n
(e) Resin 1j
(f) Resin 1l
(g) Resin 1m
(h) Resin 1n
FIGURE SI27. SCANNING ELECTRON MICROSCOPY IMAGES OF RESINS BEADS PREPARED BY USING (A) COX POROGEN,
(B,C,D) 1-CD POROGEN, AND THE CORRESPONDING MACROPOROUS RESIN FRACTURES (E-H).
Page | 189

Engineering Journal Preparation and Characterization of Cross-Linked Polymer Supports For Catalysts Immobilization

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International Journal of Engineering Research & Science (IJOER)

[Vol-2, Issue-2, February- 2016]

Preparation and characterization of cross-linked polymer

International Journal of Engineering Research & Science (IJOER)

[Vol-2, Issue-2, February- 2016]

RESULTS AND DISCUSSION

SCHEME 1. SYNTHESIS OF PS-Cl RESINS 1a-o

International Journal of Engineering Research & Science (IJOER)

[Vol-2, Issue-2, February- 2016]

FIGURE 1. FTIR ANALYSIS OF POLYMER 1a

Vetrino ATR karen

International Journal of Engineering Research & Science (IJOER)

[Vol-2, Issue-2, February- 2016]

International Journal of Engineering Research & Science (IJOER)

[Vol-2, Issue-2, February- 2016]

Average pore radius ()

International Journal of Engineering Research & Science (IJOER)

[Vol-2, Issue-2, February- 2016]

File: C:...\polimeri matteo\MA50_25 mesh.001

Rev Heat Flow (W/g)

Nonrev Heat Flow (W/g)

Heat Flow (W/g)

FIGURE 3. MTDSC ANALYSIS OF POLYMER 1n

International Journal of Engineering Research & Science (IJOER)

[Vol-2, Issue-2, February- 2016]

Typical procedure for the preparation of chloromethylated resins PS-Cl 1.

International Journal of Engineering Research & Science (IJOER)

[Vol-2, Issue-2, February- 2016]

International Journal of Engineering Research & Science (IJOER)

[Vol-2, Issue-2, February- 2016]

Supporting information for

Preparation and characterization of cross-linked polymer

General procedure for the preparation of chloromethylated resins PS-Cl 1b-o

International Journal of Engineering Research & Science (IJOER)

[Vol-2, Issue-2, February- 2016]

C:\Documents and Settings\Bruker\Desktop\misure FTIR\Polimeri luigi - fine 2012\MA57-PsCl.0

FIGURE SI1. FTIR ANALYSIS OF POLYMER 1b.

C:\Documents and Settings\Bruker\Desktop\misure FTIR\Polimeri luigi - fine 2012\SZ18_35mesh_2.0

Vetrino ATR karen

FIGURE SI2. FTIR ANALYSIS OF POLYMER 1h.

[Vol-2, Issue-2, February- 2016]

International Journal of Engineering Research & Science (IJOER)

C:\Documents and Settings\Bruker\Desktop\misure

C:\Documents and Settings\Bruker\Desktop\misure

[Vol-2, Issue-2, February- 2016]

International Journal of Engineering Research & Science (IJOER)

C:\DOCUMENTS AND SETTINGS\ADMINISTRATOR\DESKTOP\MA53.0

C:\Documents and Settings\Bruker\Desktop\misure FTIR\Polimeri luigi - fine 2012\SZ12_45mesh.0

Vetrino ATR karen

[Vol-2, Issue-2, February- 2016]

International Journal of Engineering Research & Science (IJOER)

C:\Documents and Settings\Bruker\Desktop\misure

International Journal of Engineering Research & Science (IJOER)

[Vol-2, Issue-2, February- 2016]

[Vol-2, Issue-2, February- 2016]

International Journal of Engineering Research & Science (IJOER)

Instrument type and / or accessory

Instrument type and / or accessory

ATOMS BY 1,5,7-TRIAZABICYCLO[4.4.0]DEC-5-ENE (TBD) (RED LINE).

International Journal of Engineering Research & Science (IJOER)

[Vol-2, Issue-2, February- 2016]

FIGURE SI11. PORE SIZE DISTRIBUTION OF POLYMER 1a.

FIGURE SI12. PORE SIZE DISTRIBUTION OF POLYMER 1b.