Nanoporous highly crosslinked polymer networks with covalently bonded amines for CO2 capture

Accepted Manuscript Nanoporous highly crosslinked polymer networks with covalently bonded amines for CO2 capture Jing Huang, Jie Zhu, Samuel A. Snyder, Amanda J. Morris, S. Richard Turner PII:

S0032-3861(18)30821-8

DOI:

10.1016/j.polymer.2018.08.075

Reference:

JPOL 20882

To appear in:

Polymer

Received Date: 7 July 2018 Revised Date:

28 August 2018

Accepted Date: 29 August 2018

Please cite this article as: Huang J, Zhu J, Snyder SA, Morris AJ, Turner SR, Nanoporous highly crosslinked polymer networks with covalently bonded amines for CO2 capture, Polymer (2018), doi: 10.1016/j.polymer.2018.08.075. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

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Nanoporous Highly Crosslinked Polymer Networks with Covalently

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Bonded Amines for CO2 Capture

Jing Huang,†,‡ Jie Zhu,†,‡ Samuel A. Snyder,†,‡ Amanda J. Morris,†,‡ and S. Richard Turner*,†,‡

Department of Chemistry, Virginia Tech, Blacksburg, VA 24061, United States

‡

Macromolecules Innovation Institute, Virginia Tech, Blacksburg, VA 24061, United

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States

Abstract

Amine-containing polymers are considered to be promising CO2 capture materials. Considerable research effort has been invested in designing and preparing new materials

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with high surface area materials and amine contents. In this work, a series of nanoporous highly crosslinked polymers (HCPs) with covalently bonded amines were prepared by post-modification of highly crosslinked divinylbenzene-maleic anhydride (DVB-MAH)

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copolymer with various diamines. The successful incorporation of the diamines was confirmed using Fourier transform infrared spectroscopy (FT-IR), thermogravimetric

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analysis (TGA) and elemental analysis. The resulting amine-containing HCPs possessed both micropores and mesopores, and they exhibited BET surface area of 183-500 m2/g. The CO2 capture capacity of these polymers varied in relation to their surface areas and amine contents. The chemistry described in this report provides a facile synthetic route to obtain new amine containing polymer particles as potential solid sorbents for acidic gases such as carbon dioxide.

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1. Introduction For the past decades, increasing atmospheric CO2 concentrations due to the

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combustion of fossil fuels and other anthropogenic emissions have caused public concerns.[1-3] CO2 capture and sequestration (CCS) was proposed to be an effective technology option in controlling atmospheric CO2 levels.[4] Liquid amine scrubbing is currently the most mature technology for industrial CO2 capture, the reversible reaction

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between amine groups and CO2 ensures effective and selective sorption of CO2.[5, 6] Nonetheless, due to solvent emission and degradation, equipment corrosion, and

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intensive energy-demands during regeneration, scientists and governments are shifting their attention toward new, efficient, and cost-effective materials for CO2 capture.[7, 8] In particular, porous solid sorbents, including organic, inorganic, or organic-inorganic hybrid materials, appear to be promising alternatives.[9] Various attempts have been

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made to incorporate amines onto porous solid sorbents to achieve selective CO2 sorption. For example, amines were immobilized onto mesoporous silica,[10-15] metal-organic frameworks (MOFs),[16-18] and polymer networks,[19] either physically via wet

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impregnation,[14] or covalently by grafting[10, 11, 13, 15, 17] or co-condensation[12, 19]. The disadvantages of liquid amine scrubbing can be easily overcome by using solid

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amine sorbents, and these materials exhibit fast adsorption kinetics, low operating temperatures and high selectivity.[15] However, challenges, such as low immobilized amine content, low thermal stability, and difficult multi-step syntheses, present barriers to practical CCS applications.[13, 20, 21]

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Nanoporous (pore width < 50 nm) highly crosslinked and hypercrosslinked polymers have generated increasing attention owing to their advantages such as synthetic

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ease and diversity, high surface area, good physicochemical stability, and low skeleton density.[22-27] Divinylbenzene (DVB) is one of the most commonly used crosslinking

styrenic

monomer,

DVB

could

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agents, since it provides rigid and short crosslinks. As an analogue of the electron-rich quickly

cross-propagate

and

crosslink

with

electron-deficient maleic anhydride (MAH) or maleimide monomers.[28-30] Previously we reported a two-step synthesis of carboxylic acid functionalized porous polymers via

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the deprotection of DVB-crosslinked alternating copolymer precursors. The resulting polymer networks showed high surface area and moderate CO2 capture capacity.[24] In this study, we report a facile approach to immobilize amines covalently onto nanoporous

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DVB-MAH to prepare solid amine sorbents with high amine contents. Their CO2 capture

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abilities are also explored and discussed.

2. Experimental section 2.1 Materials

Divinylbenzene (DVB, Sigma-Aldrich, technical grade, isomer of p- and m-, 80%

purity), toluene (Fisher, HPLC grade), poly(vinyl alcohol) (Sigma-Aldrich, 87-89% hydrolyzed), sodium chloride (Fisher, certified ACS crystalline), dichloromethane (DCM, anhydrous, ≥ 99.8%, Sigma-Aldrich), thionyl chloride (Sigma-Aldrich, 97%), 3

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p-phenylenediamine (Sigma-Aldrich, 99%), ethylenediamine (Sigma-Aldrich, 99%), 1,4-diaminobutane (Sigma-Aldrich, 99%), diethylenetriamine (Sigma-Aldrich, 99%), and pentaethylenehexamine (Sigma-Aldrich, 99%) were used as received without further

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purification. Maleic anhydride (MAH, Sigma-Aldrich, 99%) was recrystallized from toluene. 2, 2’-azobisisobutyronitrile (AIBN, Aldrich, 98%) was recrystallized from

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methanol. Deionized water was provided by Virginia Tech. 2.2 Instrumental characterization.

The successful incorporation of the amines was confirmed by infrared analysis

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(FT-IR, Agilent Cary 630 FT-IR Spectrometer). Elemental analysis was performed by Atlantic Microlab (Norcross, GA). The thermogravimetric analysis (TGA) of the copolymers was conducted by TA instrument model Q5000; samples were heated from 50 to 550 ºC at a heating rate of 10 ºC/min under nitrogen. SEM micrographs of the

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copolymers were obtained using a LEO (Zeiss) 1550 field emission scanning electron microscope. Nitrogen adsorption/desorption isotherms at 77 K were obtained using a Quantachrome Autosorb 1 surface area analyzer, and the samples were degassed at

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140 °C overnight before measurements. The surface areas were calculated using the Brunauer-Emmett-Teller (BET) equation. The pore sizes were determined from nitrogen

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adsorption isotherm by the two-dimensional non-local density functional theory model with heterogeneous surfaces (2D-NLDFT-HS) using the SAIEUS software. The CO2 uptakes were measured at 273 K and 298 K by a Quantachrome Autosorb 1 instrument. 2.3 Synthesis of the DVB-MAH precursor The DVB-MAH precursor was synthesized via suspension polymerization (Scheme 1). DVB (1.95 g, 15.0 mmol), and MAH (1.47 g, 15.0 mmol) were dissolved in 5 mL 4

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toluene in a 250 mL three-neck round bottom flask equipped with a mechanical stirrer, a condenser, and an N2 gas inlet. Then 250 mL of de-ionized water was added to the flask, followed by adding poly (vinyl alcohol) (0.21g) and NaCl (1.13 g). The mixture was

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purged with N2 for 15 min while stirring. AIBN (44 mg, 1.3 wt%) was added to initiate the polymerization. The suspension mixture was stirred under N2 at 80 ˚C for 24 h. The resulting polymer beads were filtered and purified using Soxhlet extraction with toluene

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and water at 85 °C for 24. The azeotrope of the two solvents ensures effective removal of unreacted monomer, poly(vinyl alcohol) and NaCl.[31] The resulting off-white beads

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were dried in vacuum oven at 50 ˚C for 24 h (72.0%-78.5%).

Scheme 1. Synthesis of the DVB-MAH precursor by suspension polymerization 2. 4 Preparation of amine-grafted DVB-MAH networks

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The DVB-MAH precursor was hydrolyzed by stirring with 0.5 N NaOH aqueous solution at 60 ˚C for 24 h. After filtration and thorough washing using DI water, the

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carboxylic acid groups of the polymer beads were restored with 0.5 N HCl solution for 2 h at room temperature. The beads were then filtered and dried in a vacuum oven for 24 h at 80 ˚C. Then the polymer was stirred with thionyl chloride at 80 ˚C for 2 h, and the excess thionyl chloride was removed by vacuum with an acid trap (0.5 N NaOH solution). The resulting acid-chloride functionalized polymer networks were immediately dispersed in excess diamine (2.0 mole eq. to theoretical acid chloride units) solutions in anhydrous

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dichloromethane. The resulting mixtures were stirred at room temperature for 24 h and then filtered and washed thoroughly by dichloromethane and 0.5 N NaOH solution. After drying in vacuum for 24 h, light brown or yellow powders were obtained. The general

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nomenclature for these copolymers, HCP-X, is employed, in which HCP stands for highly crosslinked polymer, and the letter X represents the functional groups on the surface (e.g. COOH) and different diamines A-E (Scheme 2).

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O O O O OH O

1) NaOH, H 2O, 60 ˚C, 24 h 2) HCl, H 2O, r.t., 2 h

OH

O SOCl 2

Cl Cl

HCP

80 ˚C, 2 h

H 2N

H 2N

NH 2

H N

NH 2

O NH R NH2 NH R NH

NH 2

H 2N

B H N

O

O

C H N

N H

N H

NH 2

E

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D

H 2N

O

HCP

NH 2

H 2N

A

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NH 2-R-NH2 :

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O

1) NH 2-R-NH2 DCM, r.t., 24 h 2) NaOH, H 2O

OH OH

HCP

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Highly Crosslinked Polymer (HCP)

O

Scheme 2. Preparation of amine-grafted HCP networks by post-modification of DVB-MAH. In which diamines A through E are p-phenylenediamine, ethylenediamine, 1,4-diaminobutane, diethylenetriamine, and pentaethylenehexamine, respectively.

3. Results and discussion 3.1 Synthesis and characterization. DVB-MAH copolymers of different microstructures were previously synthesized using various polymerization techniques such as suspension polymerization,[32, 33] 6

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precipitation polymerization,[34] and dispersion polymerization.[35] Among them, the nanoporous DVB-MAH copolymers were reported using suspension polymerization, in which poly(vinylpyrrolidone) was the suspension stabilizer, and a mixture of 1,4-dioxane

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and n-dodecane was used as a pore-forming diluent.[32] These copolymers showed surface area from 4 to 535 m2/g, and the average pore width was around 4.5 nm. In this work, using poly(vinyl achohol) as the stabilizer and toluene as the organic solvent and

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porogen, we were able to obtain DVB-MAH beads with a higher surface area (667 m2/g). The SEM micrograph of DVB-MAH under low magnification is shown in Figure 1a.

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Spherical structures with pore widths in the range of 10-300 µm were observed, which is typical for the products of suspension polymerization. The beads exhibited a rough surface that was observed under higher magnification. However, the narrow nanopores

b

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a

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(pore width < 5 nm) are too small to be observed under such magnification (Figure 1b).

Figure 1. SEM micrographs of DVB-MAH particles at a) low magnification (scale bar 100 µm), and b) higher magnification (scale bar 200 nm) At first, we attempted to directly incorporate amines by the reaction of amines and

anhydride groups, since theoretically anhydride rings can react with amines to form amic acids, then the amic acids can be turned to imides after heat-driven dehydration. However,

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low incorporation of nitrogen from elemental analysis showed this reaction route did not happen as we expected. After investigating the DVB-MAH beads using Fourier transform infrared (FT-IR) spectroscopy, we attributed it to the partial hydrolysis of the MAH

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groups during the suspension polymerization and the Soxhlet extraction.[32] We also attempted to recyclize the hydrolyzed MAH by heating the sample at 250 ˚C under vacuum, however, the heat caused the nanopores to collapse which resulted in a

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non-porous structure. The same nanopore collapsing under high temperature was also observed in our previous work.[24] Therefore, we utilized a two-step modification to

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ensure the existence of both nanopores and amine groups. First, the anhydride groups were converted to acid chlorides by basic hydrolysis, acidification, and chlorination with thionyl chloride. This was followed by the amidation of the acid chloride functionalized crosslinked polymers with excess of diamine.

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The FT-IR spectra are shown in Figure 2. Figure 2a illustrates the full FT-IR spectra of DVB-MAH, the hydrolyzed HCP-COOH, and the amine grafted HCP-A to HCP-E. For better observation, Figure 2b depicts the spectra of DVB-MAH and HCP-COOH in

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the wavenumber range of 3500-1600 cm-1. A broad peak at 3367 cm-1 was observed for HCP-COOH, which is attributed to the O-H stretch of the carboxylic acid. This broad

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peak was also observed in the spectrum of DVB-MAH, but less strong than in HCP-COOH, which indicates the anhydride units are partially ring-opened to the acid form during the suspension polymerization. The characteristic anhydride twin peaks at 1859 and 1781 cm-1 were observed for DVB-MAH, which corresponds to the C=O stretch of the anhydride carbonyl groups. The C=O stretch peak of the carboxylic acid at 1716 cm-1 was observed for both HCP-COOH and DVB-MAH, which further suggests

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the partial hydrolysis of the anhydride units in DVB-MAH. Figure 2c is the spectra of HCP-A to HCP-E in the range of 1700-1000 cm-1. The characteristic peaks at 1664 cm-1 (secondary amide C=O stretch), 1605 cm-1 (N-H bend) and 1085 cm-1 (C-N stretch) can

at around 3400 cm-1 (Figure 2a).

b)

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a)

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be seen.[36] Moreover, all five modified polymers showed broad amide and amine peaks

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c)

Figure 2. a) Full FT-IR spectra of DVB-MAH, HCP-COOH, and HCP-A to HCP-E; b) FT-IR spectra of DVB-MAH and HCP-COOH in the range of 3500-1600 cm-1; c) FT-IR spectra of HCP-A to HCP-E in the range of 1700-1000 cm-1. The incorporation of diamines was further confirmed by elemental analysis (Table 1). These HCPs contain 4.39-9.71 wt% of nitrogen, which are lower than the values assuming each anhydride unit is attaching to one diamine unit. The actual incorporated

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amounts of diamines A-E were calculated from the N% content. For each anhydride unit, there is approximately 0.43 amines for A, 1.00 for B, 0.59 for C, 0.66 for D, and 0.30 for E incorporated, respectively. It is likely that some acid chloride groups did not react with

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diamines, or some diamine monomers react with two acid chlorides on both primary amine ends.

The thermal stability of porous materials is important in practical applications.

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Therefore, we examined the thermal stability of the polymers using thermogravimetric analysis (TGA) (Figure 3). The DVB-MAH precursor has a 5% degradation temperature

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of 308 ˚C, while all the modified HCPs showed two-stage degradation curves. For the modified HCPs, the first weight loss starting at ca. 180 ˚C is attributed to the decomposition of the grafted diamines,[37] and possible water loss of the transformation from amic acids to imides.[38] The second stage degradation around 300 ˚C corresponds

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to the degradation of the highly crosslinked backbone.

Figure 3. TGA curves of DVB-MAH and modified HCPs. 10

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3.2 Porosity and surface area. Nitrogen adsorption/desorption isotherms of the polymers in this study are shown

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in Figure 4a. All the polymers in this work exhibited Type IV isotherms.[39] The high gas uptakes at low pressure indicate that these polymers possess micropores (pore width < 2 nm), and the hysteresis loops suggest the presence of mesopores (2 nm < pore width < 50 nm).[39, 40] The pore size distributions were assessed by the non-local density functional

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theory method (NLDFT) on nitrogen adsorption isotherms by using the SAIEUS program.[41] The calculated pore size distributions also revealed the presence of both

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micropores and mesopores (Figure 4b). Surface areas were calculated using the Brunauer-Emmett-Teller (BET) equation.[42] The detailed surface areas and pore

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volumes of the polymers are listed in Table 1.

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Figure 4. a) Nitrogen adsorption (closed symbol)/desorption (open symbol) isotherms at 77 K for the polymers in this study; b) the pore size distributions (PSD) from nitrogen isotherms at 77 K by the non-local density functional theory method (NLDFT).

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BET surface

Micro pore volume

Total pore volume (cm3/g)b

Sample H

N

area (m2/g)

(cm3/g)a

667 607 412 500 346 343

0.28 0.24 0.16 0.19 0.13 0.13

183

DVB-MAH HCP-COOH HCP-A HCP-B HCP-C HCP-D

75.83 69.78 73.71 69.42

6.79 6.71 6.34 6.82

4.39 9.71 5.93 9.38

HCP-E

70.39

6.74

8.45

298 K

273 K

0.64 0.7 0.59 0.61 0.57 0.55

0.99 1.21 1.46 1.15 1.53

0.87

0.29

0.96

0.87

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C

CO2 uptake at 1 bar (mmol/g)

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Elemental analysis (wt%)

0.06

-

0.96 1.26 0.95 1.3

a

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Table 1. Elemental analysis, porous properties, and CO2 uptakes of the HCPs Micropore volumes determined from nitrogen adsorption isotherm at P/P0 = 0.14; bTotal pore volumes determined from nitrogen adsorption isotherm at P/P0 = 0.98 As

previously

mentioned,

the

DVB-MAH

precursor

from

suspension

polymerization exhibited a surface area of 667 m2/g. After hydrolysis, the resulting

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HCP-COOH showed a slight decrease in surface area to 607 m2/g. After grafting the diamines onto the precursor, obvious decrease in surface areas was observed in all samples. In general, bulkier diamine molecules resulted in relatively lower surface area,

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and the micropore volume decreased faster than the total pore volume. The best example is HCP-E, which has the pentaethylenehexamine graft. The surface area of HCP-E

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decreased by 73% to 183 m2/g compared to DVB-MAH, and it only showed 0.06 cm3/g of micropore volume, which suggests that the grafting of bulky diamines results in blocking of micropores. However, the surface area of HCP-A only decreased to 412 m2/g although p-phenylenediamine is also a bulky diamine. This is probably because less p-phenylenediamine was incorporated, as evidenced by the low nitrogen content in elemental analysis. HCP-B is grafted with the least bulky ethylenediamine, therefore it has the highest surface area among the five modified polymers. 1,4-diaminobutane and 13

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diethylenetriamine are similar in their size, which means that HCP-C and HCP-D have close surface area, micro- and total pore volume.

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3.3 CO2 adsorption. The CO2 adsorption properties of the polymers were investigated at 273 K and 298K up to 1 bar (Figure 5). The CO2 uptakes of polymers at 1 bar are compared to their surface areas in Table 1. The precursor DVB-MAH showed CO2 uptakes of 0.99 mmol/g

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at 273 K and 0.87 mmol/g at 298 K, which is close to other polymer networks with similar surface area.[24, 43] HCP-D showed the highest CO2 uptake at both 273 K and

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298 K, even with a relatively low surface area. This suggests that the extra secondary amine groups provided favored sites for the reaction of CO2 to reversibly form carbamates.[44, 45] With similar surface area, HCP-C showed about 25% lower CO2 uptake than HCP-D at 273 K. This is likely due to the lack of secondary amine in

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1,4-diaminobutane, and the flexible 1,4-diaminobutane may facilitate the formation of amides with both terminal amine groups, which can further decrease the available sites for specific CO2 adsorption. The CO2 uptake of HCP-B was slightly lower than HCP-D,

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which is a result of both the high surface area and higher amine content. The CO2 uptake of HCP-E was close to the unmodified DVB-MAH even with such a low surface area,

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thanks to the abundant secondary amine groups in the grafted pentaethylenehexamine. However, the low surface area and pore volume limited the CO2 adsorption ability of HCP-E.

It is also worth noting that the CO2 adsorption/desorption isotherms of modified HCP-A to HCP-E all showed hysteresis. The decrease quantity of the desorbed CO2 is likely due to the strong interaction between CO2 and the amine groups, which makes the

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desorption process more difficult. Similar hysteresis effects in CO2 isotherms were previously observed for some other amine-containing materials.[46-49] a)

b)

DVB-MAH HCP-A HCP-B HCP-C HCP-D

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DVB-MAH HCP-A HCP-B HCP-C HCP-D

HCP-E

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HCP-E

298 K

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273 K

Figure 5. CO2 adsorption isotherms at a) 273 K, and b) 298 K up to 1 bar Table 2 lists the recently reported amine-containing polymers and their properties, some of them showed extraordinarily high CO2 uptakes. It is shown that the CO2 uptake

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is a result of both surface area and amine content. Among these materials, HCP-B only showed moderate CO2 uptake. However, unlike some of the polymers in this table,

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HCP-B doesn’t require expensive starting materials and complicated synthesis procedure.

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Table 2. CO2 adsorption properties of some recently reported amine-containing polymers

Surface

Amine

area

incorporation

(m2/g)

method

PPN-6-CH2DETA

555

Graft

CBAP-1 (EDA)

435

CBAP-2 (EDA)

228

XAD-4-TEPA

502

NUT-1

99.9

NUT-2

70

Material

Graft Graft Condensation

N wt% 11.95 12.89 15.54 7.22 12.14 10.97

Amine type 1°, 2° 1°, 2° 1°, 2° 2°

CO2 uptake @ 1bar (mmol/g) 273 K

298 K

-

4.3

2.99

2.2

2.88

2.05

-

1.21

1.86

1.43

-

0.99

Ref [50] [48] [51] [49]

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NUT-3

42.4

10.37

-

0.64

NUT-4

26.9

12.29

-

0.4

FC-POP-CH2NH2

939

4.1

4.2

2.5

FC-POP-CH2DETA

636

4.5

3.4

FC-POP-CH2PEI

129

3.2

2.6

amine-PIM-1

-

Reduction

5.98

1°

~1.0

-

[53]

KFUPM-1

305

Condensation

12.31

1°, 2°

1.52

1.04

[54]

PEI@DE(30,10)

769

Impregnation

8.94

1°, 2°

-

3.28

[55]

HCP-B

500

Graft

9.71

1°, 2°

1.46

1.26

This work

Graft

10.79

1°, 2°

of

amine-containing nanoporous

polymers

were

prepared

by

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A series

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4. Conclusion

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14.53

[52]

post-modification of the DVB-MAH copolymer with various diamines. High amine-contents were achieved by covalently reacting a series of multiamines with the acid-chloride functionalized polymer surface. With good thermal stability and good CO2 adsorption capacity, these amine-functionalized polymers provide new polymer particles

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for further solid sorbent studies. This work also provides an efficient strategy for grafting amine to anhydride- or carboxylic acid-functionalized polymer surfaces.

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Acknowledgement

This work was supported by the National Science Foundation (NSF) under grant DMR-0905231,

DMR-1206409,

and

DMR-1310258.

We

thank

the

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number

Macromolecules Innovation Institute and the Department of Chemistry at Virginia Tech for support.

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Highlights: - Nanoporous highly crosslinked divinylbenzene-maleic anhydride (DVB-MAH) copolymer was synthesized using suspension polymerization with BET surface area of 667 m2/g - Multiamines are covalently bonded to nanoporous DVB-MAH by a two-step post-modification. - The amine-containing polymers have surface areas of 183-500 m2/g and with considerable CO2 uptakes.