Preparation and characterization of cross-linked polymer ...Preparation and characterization of...

International Journal of Engineering Research & Science (IJOER) ISSN: [2395-6992] [Vol-2, Issue-2, February- 2016]

Page | 166

Preparation and characterization of cross-linked polymer

supports for catalysts immobilization Maria P. Bracciale

1, Alessandra Broggi

2*, Elena Bartollini

3, Francesca Sbardella

4, Matteo

Poldi5, Assunta Marrocchi

6*, Maria L. Santarelli

7*, Luigi Vaccaro

8*

1,2,4,5,7

Dipartimento di Ingegneria Chimica Materiali Ambiente, Università di Roma “La Sapienza”, Via Eudossiana 18, 00185

Roma, Italy;

3,6,8

Laboratory of Green Synthetic Organic Chemistry, Dipartimento di Chimica, Università 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 (µ-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 (μ-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 μ-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. RESULTS AND DISCUSSION

2.1 Resins preparation.

The synthesis of resins 1a-o was performed by α,α′-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

+ Cl

Porogen

AIBN 1% w/w

Aqueous phase

85°C, 24h

2 3

4

1a-o

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 (4-

vinylbenzylchloride/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 µm 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 µm).


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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 aPVA1= poly(vinyl alcohol) (MW 13.000-23.000); PVA4= poly(vinyl alcohol) (MW 85.000-124.000); 2-EHA= 2-

ethylhexanoic 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.

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 cm−1

corresponds to the stretching vibration of C–Cl bond,

and the band at 1421 cm−1

is corresponding to the bending vibration of -CH2 in –CH2Cl. Besides, the IR spectra exhibited

two peaks at 1265 cm−1

and 823 cm−1

, which were attributed to the vibration absorptions of =C–H bond of the –CH2Cl p-

substituted 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].

C:\Documents and Settings\Bruker\Desktop\misure FTIR\Polimeri luigi - fine 2012\G185_35mesh.0 Vetrino ATR karen P-ATR V70 11/12/2012

3352.2

6

3018.6

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2919.8

6

1701.8

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1606.6

9

1510.9

81485.4

71443.9

51421.2

01359.5

9

1265.1

8

1212.4

81181.9

41143.2

01091.8

9

1016.2

9

909.6

3

819.2

6

709.6

4674.4

1638.5

6

553.5

4

436.2

2415.1

9

5001000150020002500300035004000

Wavenumber cm-1

0.0

10

.02

0.0

30

.04

0.0

50

.06

0.0

7

Ab

so

rba

nce

Un

its

Page 1/1

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 μ-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 OF–CL GROUPS (A-C). OPTICAL MICROSCOPY

IMAGES 15X (D-F) SHOWING THE HALF-CUT BEAD MAPPING TRACE. ALL SPECTRA WERE COLLECTED IN REFLECTION

MODE WITH A 3 cm−1

SPECTRAL RESOLUTION, AND THE IMAGES WERE OBTAINED BY MONITORING THE PEAK CENTRED AT

675 cm−1

; THE ABSORPTION INTENSITY WAS MEASURED AND EXPRESSED AS ARBITRARY UNITS.

In order to observe the active site spatial distribution, the peak centered at 675 cm−1

(i.e. C–Cl 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 1,5,7-

triazabicyclo[4.4.0]dec-5-ene (TBD) base in dioxane at 60°C [20]. The μ-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.

Brunauer–Emmett–Teller (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 12-

13, Table 2), high values of surface area were obtained (107.1 m2/g and 78.3 m

2/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

Å and 396 Å, 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

Entry Polymer Surface area (m2/g) Average pore volume (cm

3/g) Average pore radius (Å)

1 1a 5.0 0.0188 77

2 1b 27.2 0.29 85

8 1h 3.4 0.02 107

9 1i 0.3 10-3

8

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 m

2/g,

respectively) and average pore radius (77 Å and 85 Å, 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 30-250°C (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 ~220°C

(Figure 3).


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0.08

0.09

0.10

0.11

No

nre

v H

ea

t F

low

(W

/g)

0.14

0.16

0.18

0.20

0.22

Re

v H

ea

t F

low

(W

/g)

0.24

0.26

0.28

0.30

0.32

He

at

Flo

w (

W/g

)

50 100 150 200 250 300

Temperature (°C)

Sample: MA50_25 meshSize: 8.2000 mgMethod: metodo vaccaro

DSCFile: C:...\polimeri matteo\MA50_25 mesh.001Operator: TA GFRun Date: 24-Jan-2013 13:04Instrument: 2920 MDSC V2.6A

Exo Down 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 SI26-

27). 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. EXPERIMENTAL SECTION

3.1 General.

All the commercially available chemicals were purchased at Sigma–Aldrich 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 Fison’s 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 4000–400 cm-1

,

resolution 4 cm-1

, equipped with single reflection diamond ATR cell.

µ-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 µ-FTIR imaging, spectra were collected, in reflection mode, in the mid-infrared (MIR) range of

600–4000 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.

Brunauer–Emmett–Teller (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 85,000–124,000, 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), 2-

ethylhexanoic 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 (μ-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 Università degli Studi di Perugia, and the Ministero dell’Istruzione, dell’Università 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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http://pubs.acs.org/doi/abs/10.1021/ar960248m

http://pubs.acs.org/doi/abs/10.1021/ar960248m

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http://pubs.acs.org/doi/abs/10.1021/ma951606o




Page | 174

Supporting information for

Preparation and characterization of cross-linked polymer

supports for catalysts immobilization Maria P. Bracciale

1, Alessandra Broggi

2*, Elena Bartollini

3, Francesca Sbardella

4, Matteo

Poldi5, Assunta Marrocchi

6*, Maria L. Santarelli

7*, Luigi Vaccaro

8*

1,2,4,5,7

Dipartimento di Ingegneria Chimica Materiali Ambiente, Università di Roma “La Sapienza”, Via Eudossiana 18, 00185

Roma, Italy; 3,6,8

Laboratory of Green Synthetic Organic Chemistry, Dipartimento di Chimica, Università degli Studi di

Perugia, Via Elce di Sotto 8, 06123 Perugia, Italy.

e-mail: [email protected]; [email protected]; [email protected];

[email protected]

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 85,000–124,000, 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 85,000–124,000, 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 85,000–124,000, 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 85,000–124,000, 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 85,000–124,000, 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: 1-

chlorodecane (1-CD); Stabilizer: poly(vinyl alcohol) (MW 85,000–124,000, 99% hydrolyzed) (0.1%) (yield 71%).

PS-Cl 1l. Prepared by following the procedure described in the Experimental Section, Main Text, for 1a. Porogen: 1-

chlorodecane (1-CD); Stabilizer: poly(vinyl alcohol) (MW 85,000–124,000, 99% hydrolyzed) (0.4%) (yield 68%).

PS-Cl 1m. Prepared by following the procedure described in the Experimental Section, Main Text, for 1a. Porogen: 1-

mailto:[email protected]


Page | 175

chlorodecane (1-CD); Stabilizer: poly(vinyl alcohol) (MW 85,000–124,000, 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: 1-

chlorodecane (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-

chlorodecane (1-CD); Stabilizer: poly(vinyl alcohol) (MW 13,000-23,000, 99% hydrolyzed) (0.1%) (yield 70%).

C:\Documents and Settings\Bruker\Desktop\misure FTIR\Polimeri luigi - fine 2012\MA57-PsCl.0 Rigaglia Davide rigaglia davide 11/12/2012

332

7.4

5

301

5.4

0

291

4.8

6

169

2.8

3

160

5.7

7

151

0.7

6

144

2.5

9142

0.5

2135

9.0

0

126

4.8

0

121

1.4

4

108

8.0

9

101

5.6

0

907

.98

815

.36

708

.18

672

.33

637

.89

540

.44

475

.62

446

.72

416

.99

5001000150020002500300035004000

Wavenumber cm-1

0.0

10

0.0

20

0.0

30

0.0

40

Ab

so

rba

nce

Un

its

Page 1/1

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 P-ATR V70 11/12/2012

333

0.6

8

302

4.0

6

291

8.8

9

232

2.8

4

160

2.6

1

151

0.6

3149

2.6

8144

2.6

7142

0.6

7

126

4.4

0

108

8.9

1

101

7.2

0

907

.47

819

.60

747

.15

700

.00

672

.07

540

.17

409

.20

5001000150020002500300035004000

Wavenumber cm-1

0.0

05

0.0

10

0.0

15

0.0

20

Ab

so

rba

nce

Un

its

Page 1/1

FIGURE SI2. FTIR ANALYSIS OF POLYMER 1h.


Page | 176

C:\Documents and Settings\Bruker\Desktop\misure FTIR\Polimeri luigi - fine 2012\F46_25mesh.0 Vetrino ATR karen P-ATR V70 11/12/2012

302

0.2

9

292

0.8

7285

0.6

3

232

3.1

7

170

1.1

2

162

9.1

9160

4.5

5

151

0.2

1148

5.7

8144

2.9

3142

0.6

0135

7.6

6131

2.5

9

126

4.6

4

121

3.0

2118

2.6

5

109

5.0

9

101

8.0

0989

.70

905

.57

824

.37

798

.80

745

.07

709

.47

673

.00

638

.20

549

.83

424

.51

404

.65

5001000150020002500300035004000

Wavenumber cm-1

0.0

10

.02

0.0

30

.04

0.0

50

.06

Ab

so

rba

nce

Un

its

Page 1/1

FIGURE SI3. FTIR ANALYSIS OF POLYMER 1i.

C:\Documents and Settings\Bruker\Desktop\misure FTIR\Polimeri luigi - fine 2012\MA52-PsCl.0 Rigaglia Davide rigaglia davide 11/12/2012

333

1.9

1

301

5.7

4

291

6.6

4285

3.7

6

235

6.6

4234

4.6

2232

5.4

3

170

1.4

5

160

6.6

7

151

0.4

1148

5.3

9144

2.7

2142

0.6

0136

2.5

8

126

4.5

5

121

1.5

6

103

7.9

9101

4.7

7

908

.93

815

.77

708

.97

675

.14

668

.68

638

.73

540

.83

467

.46

437

.86

405

.48

5001000150020002500300035004000

Wavenumber cm-1

0.0

10

0.0

15

0.0

20

0.0

25

0.0

30

0.0

35

0.0

40

Ab

so

rba

nce

Un

its

Page 1/1

FIGURE SI4. FTIR ANALYSIS OF POLYMER 1j.


Page | 177

C:\DOCUMENTS AND SETTINGS\ADMINISTRATOR\DESKTOP\MA53.0 Rigaglia Davide rigaglia davide 11/12/2012

3313.5

1

3021.9

4

2918.8

1

2362.5

22342.9

72324.5

8

1703.6

1

1610.4

0

1510.5

8

1442.7

91420.8

2

1318.6

6

1264.8

3

1212.9

3

1142.8

7

1092.7

5

1017.2

2

911.5

0

820.0

1

708.8

1672.4

5638.1

5

549.2

1

475.2

1

411.1

5

5001000150020002500300035004000

Wavenumber cm-1

0.0

05

0.0

10

0.0

15

0.0

20

Ab

so

rba

nce

Un

its

Page 1/1

FIGURE SI5. FTIR ANALYSIS OF POLYMER 1l.

C:\Documents and Settings\Bruker\Desktop\misure FTIR\Polimeri luigi - fine 2012\SZ12_45mesh.0 Vetrino ATR karen P-ATR V70 11/12/2012

332

5.6

7

302

4.7

6

291

9.4

0

160

2.6

3

151

0.7

3149

2.5

7144

5.3

8142

1.3

0

132

7.9

8

126

4.6

6

114

3.0

8

109

4.3

5

101

7.9

4

909

.06

823

.34

759

.87

699

.51

674

.88

541

.95

5001000150020002500300035004000

Wavenumber cm-1

0.0

20

.04

0.0

60

.08

0.1

0

Ab

so

rba

nce

Un

its

Page 1/1

FIGURE SI6. FTIR ANALYSIS OF POLYMER 1m.


Page | 178

C:\Documents and Settings\Bruker\Desktop\misure FTIR\Polimeri luigi - fine 2012\MA50_25mesh.0 Vetrino ATR karen P-ATR V70 11/12/2012

3362.0

1

3021.9

6

2921.5

0

2323.5

2

1610.9

2

1510.7

41485.6

71443.1

81421.1

1

1264.8

2

1212.9

91182.9

6

1111.4

2

1017.9

1

911.1

4

822.7

1

744.4

1708.6

1672.3

0638.2

3

554.5

8

427.2

0415.9

1

5001000150020002500300035004000

Wavenumber cm-1

0.0

10

.02

0.0

30

.04

Ab

so

rba

nce

Un

its

Page 1/1

FIGURE SI7. FTIR ANALYSIS OF POLYMER 1o.


Page | 179

(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 OF–Cl GROUPS (A-E). OPTICAL MICROSCOPY

IMAGES 15X (F-J) SHOWING THE HALF-CUT BEAD MAPPING TRACE.


Page | 180

C:\Documents and Settings\Bruker\Desktop\misure FTIR\Polimeri luigi - fine 2012\MA58-PsTBD.0 MA58 Instrument type and / or accessory

C:\Documents and Settings\Bruker\Desktop\misure FTIR\Polimeri luigi - fine 2012\MA41-PsCl.0 MA41_2 Instrument type and / or accessory

16/04/2013

17/04/2013

3354.6

7

3211.3

1

3009.7

6

2918.0

52916.1

42854.5

5

2354.5

22323.8

4

2167.1

02162.7

02112.9

62050.5

42050.3

32015.3

21980.8

41980.6

11915.8

61905.3

51790.4

21698.7

4

1609.2

61595.4

4

1509.4

61486.2

21443.8

51442.5

41420.7

61420.3

61369.9

31359.6

41314.1

61302.9

51264.3

41205.7

41182.2

31111.6

61087.1

51049.2

21016.6

9908.2

5882.6

5819.4

7807.7

9752.3

7708.4

9672.9

5633.2

5

551.5

0

462.3

3420.5

4406.3

8

5001000150020002500300035004000

Wavenumber cm-1

0.0

30.0

40.0

50.0

60.0

70.0

80.0

9

Absorb

ance U

nits

Page 1/1

FIGURE SI9. FTIR ANALYSIS OF POLYMER 1l (BLU LINE) AND 1l AFTER NUCLEOPHILIC SUBSTITUTION OF THE CHLORINE

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

0

0.45

0.22

0.2

0.18

0.16

0.12

0.1

0.08

0.06

0.04

0.02

0.24

0.26

0.28

0.3

0.32

0.34

0.36

0.38

0.4

0.42

500 1000 15001397-1366 x-axis [µm]

500

1000

1500

y-a

xis

[µ

m]

(a) (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 | 181

FIGURE SI11. PORE SIZE DISTRIBUTION OF POLYMER 1a.

FIGURE SI12. PORE SIZE DISTRIBUTION OF POLYMER 1b.


Page | 182

FIGURE SI13. PORE SIZE DISTRIBUTION OF POLYMER 1h.

FIGURE SI14. PORE SIZE DISTRIBUTION OF POLYMER 1i.


Page | 183

FIGURE SI15. PORE SIZE DISTRIBUTION OF POLYMER 1j.

FIGURE SI16. PORE SIZE DISTRIBUTION OF POLYMER 1l.


Page | 184

FIGURE SI17. PORE SIZE DISTRIBUTION OF POLYMER 1m.

FIGURE SI18. PORE SIZE DISTRIBUTION OF POLYMER 1n.


Page | 185

0.16

0.17

0.18

0.19

0.20

0.21

0.22

0.23

0.24

0.25

0.26

0.27

0.28

0.29

No

nre

v H

ea

t F

low

(W

/g)

0.10

0.11

0.12

0.13

0.14

0.15

0.16

0.17

0.18

0.19

0.20

Re

v H

ea

t F

low

(W

/g)

0.20

0.23

0.26

0.29

0.32

0.35

0.38

0.41

0.44

0.47

0.50

He

at

Flo

w (

W/g

)

50 100 150 200 250 300

Temperature (°C)

Sample: G185_45 meshSize: 4.2000 mgMethod: metodo vaccaro

DSCFile: E:...\polimeri matteo\G185_45 mesh.001Operator: TA GFRun Date: 24-Jan-2013 16:42Instrument: 2920 MDSC V2.6A


FIGURE SI19. MTDSC ANALYSIS OF POLYMER 1a.

0.2062

0.2125

0.2187

0.2250

0.2312

0.2375

0.2437

0.2500

0.2562

0.2625

0.2687

0.2750

0.2812

0.2875

0.2937

No

nre

v H

ea

t F

low

(W

/g)

0.1000

0.1062

0.1125

0.1188

0.1250

0.1312

0.1375

0.1437

0.1500

0.1562

0.1625

0.1687

0.1750

0.1812

0.1875

0.1937

0.2000

Re

v H

ea

t F

low

(W

/g)

0.3000

0.3062

0.3125

0.3188

0.3250

0.3312

0.3375

0.3437

0.3500

0.3562

0.3625

0.3687

0.3750

0.3812

0.3875

0.3937

0.4000

He

at

Flo

w (

W/g

)

50 100 150 200 250 300

Temperature (°C)

Sample: G185_45 meshSize: 4.2000 mgMethod: metodo vaccaro

DSCFile: C:...\polimeri matteo\G185_45 mesh.001Operator: TA GFRun Date: 24-Jan-2013 16:04Instrument: 2920 MDSC V2.6A


FIGURE SI20. MTDSC ANALYSIS OF POLYMER 1b.


Page | 186

0.059

0.063

0.067

0.071

0.075

0.079

0.083

0.087

0.091

No

nre

v H

ea

t F

low

(W

/g)

0.12

0.14

0.16

0.18

0.20

0.22

0.24

Re

v H

ea

t F

low

(W

/g)

0.18

0.19

0.20

0.21

0.22

0.23

0.24

0.25

0.26

0.27

0.28

0.29

0.30H

ea

t F

low

(W

/g)

80 100 120 140 160 180 200 220 240

Temperature (°C)

Sample: SZ18_230714Size: 11.8000 mgMethod: metodo vaccaro

DSCFile: E:...\DSC nuovi\230714\SZ18_230714.001Operator: mlsRun Date: 23-Jun-2014 14:51Instrument: 2920 MDSC V2.6A


FIGURE SI21. MTDSC ANALYSIS OF POLYMER 1h.

0.14

0.16

No

nre

v H

ea

t F

low

(W

/g)

0.080

0.085

0.090

0.095

0.100

0.105

0.110

0.115

0.120

Re

v H

ea

t F

low

(W

/g)

0.10

0.12

0.14

0.16

0.18

0.20

0.22

0.24

0.26

0.28

0.30

0.32

0.34

0.36

0.38

0.40

He

at

Flo

w (

W/g

)

80 100 120 140 160 180 200 220 240

Temperature (°C)

Sample: F46_230714Size: 8.0000 mgMethod: metodo vaccaro

DSCFile: E:...\DSC nuovi\230714\F46_230714.001Operator: mlsRun Date: 23-Jun-2014 10:13Instrument: 2920 MDSC V2.6A


FIGURE SI22. MTDSC ANALYSIS OF POLYMER 1i.


Page | 187

0.04

0.07

0.10

0.13

0.16

0.19

0.22

0.25

0.28

No

nre

v H

ea

t F

low

(W

/g)

0.15

0.18

0.21

0.24

0.27

0.30

Re

v H

ea

t F

low

(W

/g)

0.20

0.24

0.28

0.32

0.36

0.40

He

at

Flo

w (

W/g

)

0 50 100 150 200 250 300

Temperature (°C)

Sample: MA52Size: 6.9000 mgMethod: metodo vaccaro

DSCFile: C:...\Utente FSC\Desktop\MA52.001Operator: TA GFRun Date: 20-Feb-2013 15:02Instrument: 2920 MDSC V2.6A


FIGURE SI23. MTDSC ANALYSIS OF POLYMER 1j.

0.14

0.18

0.22

0.26

0.30

0.34

0.38N

on

rev H

ea

t F

low

(W

/g)

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

Re

v H

ea

t F

low

(W

/g)

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60

He

at

Flo

w (

W/g

)

0 50 100 150 200 250 300

Temperature (°C)

Sample: MA49Size: 2.6000 mgMethod: metodo vaccaro

DSCFile: E:\MA53.001Operator: TA GFRun Date: 20-Feb-2013 12:41Instrument: 2920 MDSC V2.6A


FIGURE SI24. MTDSC ANALYSIS OF POLYMER 1l.


Page | 188

0.086

0.092

0.098

0.104

0.110

0.116

0.122

0.128

0.134

0.140

0.146

No

nre

v H

ea

t F

low

(W

/g)

0.06

0.11

0.16

0.21

0.26

Re

v H

ea

t F

low

(W

/g)

0.20

0.25

0.30

0.35

0.40

He

at

Flo

w (

W/g

)

140 160 180 200 220 240

Temperature (°C)

Sample: SZ12_230714Size: 9.2000 mgMethod: metodo vaccaro

DSCFile: E:...\DSC nuovi\230714\SZ12_230714.001Operator: mlsRun Date: 23-Jun-2014 13:08Instrument: 2920 MDSC V2.6A


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 | 189

(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).

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