Modifications of addition poly(5-vinyl-2-norbornene) and gas-transport properties of the obtained polymers

Journal Pre-proof Modifications of addition poly(5-vinyl-2-norbornene) and gastransport properties of the obtained polymers

Alyona I. Wozniak, Evgeniya V. Bermesheva, Fedor A. Andreyanov, Ilya L. Borisov, Danil P. Zarezin, Danila S. Bakhtin, Natalia N. Gavrilova, Igor R. Ilyasov, Mikhail S. Nechaev, Andrey F. Asachenko, Maxim A. Topchiy, Alexey V. Volkov, Eugene Sh. Finkelshtein, Xiang-Kui Ren, Maxim Bermeshev PII:

S1381-5148(19)31306-9

DOI:

https://doi.org/10.1016/j.reactfunctpolym.2020.104513

Reference:

REACT 104513

To appear in:

Reactive and Functional Polymers

Received date:

7 December 2019

Revised date:

28 January 2020

Accepted date:

28 January 2020

Please cite this article as: A.I. Wozniak, E.V. Bermesheva, F.A. Andreyanov, et al., Modifications of addition poly(5-vinyl-2-norbornene) and gas-transport properties of the obtained polymers, Reactive and Functional Polymers (2019), https://doi.org/10.1016/ j.reactfunctpolym.2020.104513

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© 2019 Published by Elsevier.

Journal Pre-proof

Modifications of addition poly(5-vinyl-2-norbornene) and gas-transport properties of the obtained polymers Alyona I. Wozniak,a Evgeniya V. Bermesheva, a, b Fedor A. Andreyanov, a Ilya L. Borisov,a Danil P. Zarezin,a Danila S. Bakhtin,a Natalia N. Gavrilova,c Igor R. Ilyasov,b Mikhail S. Nechaev,a, d Andrey F. Asachenko, a, d Maxim A. Topchiy,a, d Alexey V. Volkov,a Eugene Sh. Finkelshtein, a Xiang-Kui Ren,e Maxim Bermesheva, c, d*

a

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A.V. Topchiev Institute of Petrochemical Synthesis of Russian Academy of Scie nces, 29 Leninsky prospekt, 119991 Moscow, Russia b I.M. Sechenov First Moscow State Medical University, 119991 Moscow, Trubetskaya str., 8, building 2, Russian Federation c D.I. Mendeleev University of Chemical Technology of Russia, 9 Miusskaya sq. ,125047 Moscow, Russia d

M. V. Lomonosov Moscow State University, 119991 Moscow, Leninskie Gory 1 (3), Russia School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, P. R. China

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Alyona I. Wozniak: Visualization, Investigation. Evgeniya V. Bermesheva: Visualization, Investigation. Fedor A. Andreyanov: Visualization, Investigation. Ilya L. Borisov: Investigation. Danil P. Zarezin: Investigation. Danila S. Bakhtin: Investigation. Natalia N. Gavrilova: Investigation. Igor R. Ilyasov: Formal analysis, Data Curation. Mikhail S. Nechaev: Investigation. Andrey F. Asachenko: Investigation. Maxim A. Topchiy: Investigation. Alexey V. Volkov: Writing - Review & Editing, Validation. Eugene Sh. Finkelshtein: Writing- Reviewing and Editing, Validation; Xiang-Kui Ren: Validation, Methodology. Maxim Bermeshev: Validation, Writing - Original Draft, Conceptualization.

*

Corresponding author. E-mail address: [email protected] (M.V. Bermeshev).

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ABSTRACT: Herein four modified polymers were prepared from readily available addition poly(5-vinyl-2-norbornene) (PVNB) and their gas-transport properties were studied in detail. Hydrogenation, epoxidation, cyclopropanation and thiol-en reactions were chosen for the modifications of PVNB. Hydrogenation of PVNB was performed using p-toluenesulfonyl hydrazide. Epoxidation of PVNB was realized employing m-chloroperoxybenzoic acid. Cyclopropanation of PVNB was carried out using diazomethane in the presence of a Pd-catalyst. For thiol-en reaction, thioacetic acid was applied as the source of a thiol and AIBN as an initiator. All listed modifications were performed in high yields (≥80%) without the destruction of polymer main chains. The degree of functionalizations was up to 99%. The influence of these modifications on the properties of the resulting polymers was evaluated. Cyclopropanation and hydrogenation of PVNB led to an enhancement of gas permeability with minimal decrease in selectivity, while epoxidation or thioacetylation gave a substantial increase in CO 2 /N 2 selectivity with decrease in permeability. The modified polymers with polar side-groups exhibited attractive selectivities for CO 2 /N2 , CO 2 /CH4 and H2 /N 2 gas separations.

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KEYWORDS: norbornenes; addition polymerization; post-polymerization reactions; micro- and mesoporous materials; CO2 /N2 -membrane; gas permeability.

Journal Pre-proof 1. Introduction Modifications of polymers are easy and fruitful ways to tune the properties of polymeric materials. Polymers containing C-C-double bonds in the main chains or in substituents are convenient objects for different functionalizations due to the versatility of alkene’s chemistry. Modifications of double bonds within main chains may be complicated by steric hindrances and the quantitative conversion of double bonds into desired functional groups is often difficult to be achieved [1-5]. At the same time, the double bonds in the side substituents as a rule are more sterically available and therefore can be more readily engaged into chemical transformations. The initial unsaturated polymers for such functionalizations can be readily prepared by

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polymerization of commercially available dienes (butadiene, isoprene, etc.) [6-8], ROMP [9] and ADMET [10] polymerization of cycloalkenes or dienes, vinyl-addition polymerization of strained cycloalkenes bearing additional C-C-double bonds in substituents [11] (like 5-vinyl-2[12-15],

5-ethylidene-2-norbornene

[15-17],

dicyclopentadiene

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norbornene

[18-20]).

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Polymerization of strained cycloalkenes is a powerful synthetic tool to prepare various polymers due to the unusual ability of these monomers to be polymerized via different ways [11, 21, 22].

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Among strained cycloalkenes, norbornene derivatives attract much attention of research groups owing to their synthetic availability and a broad scope for the targeted design of polymeric

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materials [11, 21, 23-27]. For example, starting from the bifunctional cycloalkene monomer 5ethyledene-2-norbornene (Scheme 1), it is possible to prepare the polymer with unsaturated main

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chain and the polymer with saturated backbone bearing unsaturated side chains [15, 17, 28, 29].

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The way of polymerization is determined by the catalyst nature. Vinyl-addition polymerization of norbornene derivatives provides the formation of high Tg polymers with saturated rigid backbone, which possess good thermal and chemical stability [11, 21, 30-34]. Despite these advantages of vinyl-addition polynorbornenes, little is known about their functionalizations [11, 12, 23, 35-38].

[Pd], [Ni] vinyl-addition polymerization

n

R+ cationic polymerization

[Ru] metathesis polymerization

n

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Journal Pre-proof Scheme 1. The ways of norbornenes polymerization. Recently Albeniz with coworkers described the preparation and modifications of bromoalkyl- and bromoaryl-substituted polynorbornenes [23, 35, 36]. The modified polymers were shown to be attractive supports for different catalysts. Bell et al. and He with coworkers reported the synthesis of metal-free solid anion exchange membranes for the next generation fuel cells by post-polymerization modifications of addition polynorbornenes with amines followed by alkaline treatment [33, 39]. The synthesis of high Tg sulfonated polynorbornenes ionomers via thioacetylation followed by oxidation [37] was described by Pierre et al. Claverie with coworkers have prepared thermosets displaying the high Tg values and excellent mechanical properties from addition poly(5-vinyl-2-norbornene) by epoxidation of double bonds in side

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groups and crosslinking of the formed products with polyfunctional amines, polyols, or carboxylic acids [12]. Taking into account industrial availability of 5-vinyl-2-norbornene and

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previously described opportunities in the creation of effective membrane materials based on polynorbornenes [40-46], herein we have performed four different modifications of addition

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polymer based on 5-vinyl-2-norbornene (Scheme 2) and estimated the influences of these transformations on the properties of the prepared materials (i.e. porosity, thermal stability, gas-

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transport characteristics and others).

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O n

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S

O

Scheme 2. Modifications of PVNB.

2. Experimental section 2.1. Materials All chemicals were purchased from Sigma-Aldrich and used without an additional purification. CCl4 and CHCl3 were dried with CaH2 and distilled under argon. O-xylene was distilled over metal sodium under argon. The syntheses were carried out under argon using

Journal Pre-proof standard Schlenk technique. PVNB and addition poly(5-ethylidene-2-norbornene) (PENB) samples were prepared according to [47].

2.2. Methods of polymer characterization NMR spectra (Fig. S1-S10) were recorded by spectrometer "Bruker AvancerT M DRX400" at 400.1 MHz for 1 H spectra and 100.6 MHz for

13

C spectra. Reflection IR spectra were

measured on a Bruker HYPERION 2000 microscope coupled with an IFS-66 v/s FTIR spectrometer. Calorimetric measurements were conducted using differential scanning calorimeter "Mettler" TA-4000 at heating rate 20 ºC/min under argon. The molecular masses of polymers were estimated by means of gel permeation chromatography (GPC) using high-pressure

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chromatograph "Waters" with refractometric detector; column Microgel mix 1-5 mcm 500 mm x 7.7 mm Chropack; the solvent was chloroform, sample volume 100 mkl, concentration 1 mg/ml

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(Fig. S11-S14). X-ray diffraction (WAXD) data were obtained using two-coordinate AXS detector (Bruker) and Cu Kα emission (wavelength of 0.154 nm).

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The characteristics of the porous structure of the samples were calculated from the isotherms of low temperature nitrogen adsorption/desorption. The studies were carried out using

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a Gemini VII analyzer (Micromeritics, USA) provided by the Mendeleev Center for Shared Use. The samples were degassed at 100 °C at 3.33−6.66 Pа for 10 h before measurements. The

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specific surface area was determined by the BET method. The overall volume of pores was found from a maximum value of relative pressure of 0.995. The volume of mesopores and the

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distribution of mesopore volume over sizes were determined by the BJH method. Volume of

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micropore was estimated using Dubinin-Radushkevich equation. t-Method was used for the calculation of volume and surface area of micropore. The density of synthesized polymers was measured in methanol using the hydrostatic weighting method.

2.3. Film preparation The polymer films for gas permeation measurements were prepared by casting from the 5 mass. % toluene (for H-PVNB, Cp-PVNB and S-PVNB) or chloroform (for O-PVNB) solution of a polymer. The solution was poured into a steel cylinder with diameter of 7 cm having stretched cellophane bottom. The solvent was allowed to evaporate slowly at room temperature to yield the desired polymer films. After the formation of the films cellophane was removed, and the films were dried under vacuum at room temperature up to a constant weight. A thermal treatment was not applied. The thickness of films formed was in the range of 100-120 µm. Properties of the obtained membranes were measured immediately after evacuation. The time of sample exploration was 2 days.

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2.4. Measurements of gas-transport properties Gas permeability and diffusion coefficients of gases were determined according to Daynes-Barrer technique using precise unit “Helmholtz-Zentrum Geesthacht” mounted with pressure sensor Baratron (MKS Instruments, accuracy 10-7 bar) at 30°С. Permeability coefficient is given in Barrers. Sorption coefficient was calculated as permeability coefficient ratio to diffusion coefficient.

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2.5. Cyclopropanation of PVNB

To a solution of PVNB (1.0 g, 8.33 mmol monomer units) in THF (150 ml) was added

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palladium (II) acetate (20 mg, 0.09 mmol, 0.011 eq.). The resulting solution was cooled to 15°C. Then an ether solution of diazomethane (120 ml, obtained from 10.0 g of N-nitroso-N-

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methyl urea [48]) was added dropwise to the reaction mixture. The solution was stirred during 2 hours at this temperature, then it was heated to room temperature and was stirred additionally for

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24 hours. Then reaction mixture was evaporated in vacuum to give a grayish solid. After that, the polymer was dissolved in chloroform, precipitated by methanol, and dried under reduced

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pressure (0.05 mmHg) at 80−90 °C up to the constant weight. The procedure was repeated twice. Yield: 1.1 g (99%). 13

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H NMR (CDCl3 ; δ, ppm): 3.5−0.48 m (14 H). С NMR (CDCl3 ; δ, ppm): 55.78−30.72 m, 18.52-17.59 m, 15.13-10.41 m, 8.33-0.22 m.

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IR (ATR, cm-1 ): 812 (s), 880 (vs), 1013 (vs), 1284 (m), 1454 (m), 2872 (m), 2939 (s), 2998 (m), 3071 (m).

2.6. Epoxidation of PVNB PVNB (0.883 g, 7.36 mmol monomer units) was placed into a two-necked flask equipped with a magnetic stirrer. The flask was evacuated and filled with argon. Then absolute chloroform (65 ml) was added to the flask and the mixture was stirred until PVNB was completely dissolved (about 2 h). 3-Chlorobenzoic acid (MCPBA, 70 mass.%, 2.72 g, 11.04 mmol) was added to the polymer solution and the reaction mixture was stirred for 3 hours at room temperature. The reaction was then poured into ethanol containing 2.5 ml of triethylamine. The precipitated white polymer was filtered off, washed with ethanol until neutral pH and dried under reduced pressure (0.05 mmHg) up to the constant weight. After that, the polymer was dissolved in absolute

Journal Pre-proof chloroform, precipitated by ethanol, and dried under reduced pressure (0.05 mmHg) up to the constant weight. The procedure was repeated twice. Yield: 0.83 g (83%). 1

H NMR (CDCl3 ; δ, ppm): 4.0−0.5 m (12 H).

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С NMR (CDCl3 ; δ, ppm): 59.4–26.6 m.

IR (ATR, cm-1 ): 820 (m), 875 (vs), 928 (w), 1130 (w), 1448 (w), 1479 (w), 2873 (m), 2943 (m), 3038 (w).

2.7. Hydrogenation of PVNB PVNB (1.0 g, 8.33 mmol monomer units) and p-toluenesulfonyl hydrazide (10.6 g, 56.7 mmol) were placed into a two-necked flask equipped with a magnetic stirrer and reflux

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condenser. The flask was evacuated and filled with argon. The procedure was repeated twice. Then absolute o-xylene (100 ml) was added to the flask. The reaction mixture was stirred for 3-4

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h to dissolve PVNB. The mixture was then refluxed for 15 h. After cooling the reaction mixture was poured into methanol with stirring. Resulting white polymer fibers were separated, washed

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several portions of methanol and dried under reduced pressure up to a constant weight. After that, the polymer was dissolved in toluene, precipitated into methanol, and dried under reduced

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pressure (0.05 mmHg) at 80−90 °C up to the constant weight. The procedure was repeated twice. Yield: 0.81 g (80%).

H NMR (C6 D6 ; δ, ppm): 3.5−0.48 m (14 H).

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С NMR (C6 D6 ; δ, ppm): 61.03−22.85 m, 15.16−10.15 m (CH3 ).

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IR (ATR, cm-1 ): 941 (m), 1090 (m), 928 (w), 1113 (m), 1179 (m), 1256 (m), 1375 (s), 1457 (s),

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2870 (vs), 2925 (vs), 2953 (vs).

2.8. Thioacetylation of PVNB

PVNB (0.60 g, 5.0 mmol monomer units) was dissolved in 20.0 ml of absolute CCl4 in argon atmosphere during 2-4 hours. Azobisisobutyronitrile (AIBN, 0.017 g, 0.10 mmol, 0.02 eq.) was placed into a round-bottom ampoule which was evacuated and filled with argon. Afterwards PVNB solution and thioacetic acid (0.71 ml, 0.76 g, 10.0 mmol, 2 eq.) were added to AIBN in argon atmosphere. The reaction mixture was vigorously stirred for several minutes. The ampoule was sealed and kept at 60°C for 24 h. After cooling, the reaction mixture was poured into methanol with stirring. Resulting white polymer fibers were separated, washed with methanol and dried under reduced pressure up to a constant weight. After that, the polymer was dissolved in chloroform, precipitated by methanol, and dried under reduced pressure (0.05 mmHg) at 80−90°C up to the constant weight. The procedure was repeated twice. Yield: 0.88 g (90%).

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H NMR (CDCl3 ; δ, ppm): 6.2-5.6 m (0.08 H of remaining PVNB), 5.4-4.7 m (0.16 H of PVNB

units and 0.06 H of PENB units (PENB units were formed due to the isomerization of PVNB units), 3.3−0.2 m (16 H of S-PVNB, 0.64 H of remaining PVNB, 0.66 H of PENB) 13

С NMR (CDCl3 ; δ, ppm): 196.34−194.9 m (C=O), 56.68−25.93 m.

IR (ATR, cm-1 ): 954 (m), 1109 (s), 1131 (s), 1278 (w), 1352 (m), 1426 (m), 1448 (m), 1685 (vs), 2868 (m), 2941 (m).

2.9. Thioacetylation of poly(5-ethylidene-2-norbornene) (PENB) PENB (0.10 g, 0.83 mmol monomer units) was dissolved in 3.0 ml of absolute CCl4 in argon atmosphere during 2-4 hours. Azobisisobutyronitrile (AIBN, 3.7 mg, 0.02 mmol, 0.03 eq.)

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was placed into a round-bottom ampoule which was evacuated and filled with argon. Afterwards PENB solution and thioacetic acid (0.12 ml, 1.64 mmol, 2 eq.) were added to AIBN in argon

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atmosphere. The reaction mixture was vigorously stirred for several minutes. The ampoule was sealed and kept at 80°C for 8 h. After cooling, the reaction mixture was poured into methanol at

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stirring. Resulting white polymer fibers were separated, washed with methanol and dried under reduced pressure up to a constant weight. After that, the polymer was dissolved in chloroform,

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precipitated by methanol, and dried under reduced pressure (0.05 mmHg) at 80−90°C up to the constant weight. The procedure was repeated twice. Yield: 112 mg (95%, the content of 1

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thioacetylated units was 29 mol. % according to 1 H NMR spectroscopy). H NMR (CDCl3 ; δ, ppm): 5.5−4.8 m (1H from PENB), 3.8−0.4 m (11 H from PENB and 6.44

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from S-PENB).

3. Results and discussion 3.1. Modifications of addition poly(5-vinyl-2-norbornene) The initial high-molecular weight polymer for modifications was prepared by addition polymerization of 5-vinyl-2-norbornene (PVNB, Scheme 3) using a three-component catalyst system –

N-heterocyclic

carbene

Pd-complex

activated

with Na+[B(3,5-(CF3 )2 C6 H3 )4 ]-

(NaBARF) in the presence of tricyclohexylphosphine (PCy3 ) according to the earlier developed procedure

[47,

49].

Endocyclic

norbornene double bond

was selectively involved

in

polymerization, while exocyclic double bond (in vinyl group) maintained intact (Fig. S1, S2). Cyclopropanation of the obtained polymer was carried out using diazomethane and palladium (II) acetate as a catalyst (Scheme 3, Table 1). The quantitative conversion of exocyclic double bonds into cyclopropyl groups was achieved under the mild conditions (Table 1, Fig. S5, S6, S12). The formation of cyclporopyl rings was confirmed by 1 H and

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C NMR spectroscopy.

Molecular weights of the polymer formed (Cp-PVNB) and the starting polymer (PVNB) are the

Journal Pre-proof same. The prepared Cp-PVNB showed good solubility in chloroform, aromatic hydrocarbons and THF (Table 2).

N

N Pd Cl n

Ph NaBARF, PCy3, CHCl3

CH2N2, Pd(OAc)2 THF/Et2O

n

VNB PVNB

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Cp-PVNB

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Scheme 3. Synthesis of Cp-PVNB. Epoxidation of PVNB was successfully performed in the presence of MCPBA (Scheme 13

C NMR spectroscopy the conversion of PVNB double bonds

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4, Table 1). According to 1 H and

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was quantitative (Fig. S7, S8). A little decrease in molecular weights of polymers was observed during the epoxidation. We assume the occasional destruction of polymer backbones under the

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epoxidation conditions is unlikely. The observed decrease in molecular weights (Fig. S14) is probably owing to the appearance of polar side-groups in the polymer structure and the change

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of main chain rigidity. Both these aspects can lead to a change in the size of polymer coils, since the size of polymer coils is critical for the determination of molecular weights relative to

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polystyrene standards using GPC. Therefore, molecular weights of polymers should differ according to GPC data. This suggestion is indirectly confirmed by the same values of PDI for the

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initial PVNB and the obtained O-PVNB. The isolated polymer O-PVNB was soluble in chlorinated organic solvents and in THF (Table 2). n MCPBA CHCl3

n

O O-PVNB

Scheme 4. Epoxidation of PVNB.

Journal Pre-proof Table 1 Functionalizations of PVNB. Modification Cyclopropanation Epoxidation Thioacetylation

Reaction conditions CH2 N2 , Pd(OAc)2 , THF, ()15ºC, 2 h; r.t., 24 h

Yield, %

MCPBA, CHCl3 , r.t., 3 h

83

99

Thioacetic acid, AIBN, CCl4 , 60ºC, 24 h p-TosNHNH2 ,

90

Hydrogenation

80

Mw·10-3* 720 (710) 741 (618) 1151 (710)

Mn ·10-3* 305 (310) 309 (249) 356 (310)

Mw/Mn * 2.4 (2.3) 2.4 (2.5) 3.2 (2.3)

570 (664)

259 (303)

2.2 (2.2)

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o-xylene, 140-145ºC, 15 h * - In brackets molecular weight characteristics of initial PVNB used for a modification are provided. The number average molecular weight (Mn ) and the weight average molecular weight (Mw) were determined by GPC in chloroform at 25ºC relative to polystyrene standards.

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Thioacetylation of PVNB proceeded at heating in the presence of a radical initiator (AIBN, Scheme 5, Table 1). Only 88% conversion of PVNB double bonds was achieved in this

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reaction (Fig. S9, S10). This was due to the isomerization of the vinyl-groups within PVNB into less reactive trisubstituted ethylidene-groups at heating over a source of radicals. This led to the

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formation of 5-ethylidene-2-norbornene (ENB) units within the initial polymer (Scheme 6). As

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we found the radical addition of thioacetic acid to ethylidene-moieties (thioacetylation of pure PENB) is very slow even at high temperatures (the content of thioacetylated units was 20-30 mol. % after 8-15 h of PENB thioacetylation by thioacetic acid at 80-110ºC). The attempt to

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perform thioacetylation of PVNB at a higher temperature (80ºC) led to a higher content of ENB-

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units in the resulting polymer. Therefore, the modified PVNB (S-PVNB) contained about 90 mol.% (Scheme 5). The molecular weight and molecular weight distribution became higher after

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the modification (Table 1, Fig. S13). This can be explained by side radical reactions for example like a radical recombination. The prepared S-PVNB as well as the initial PVNB displayed a good solubility in common organic solvents (Table 2). k CH C(O)SH, AIBN 3

n

m S-PVNB

o

CCl4, 60 C n : m = 95 : 5 S O

Scheme 5. Thioacetylation of PVNB.

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* CH C(O)SH, AIBN * 3

* CH C(O)SH, AIBN 3

CCl4, 60oC

*

*

CCl4, 60oC S O

Scheme 6. Isomerization of PVNB units into PENB units followed by thioacetylation reaction.

Hydrogenation of PVNB led to a saturated polymer (H-PVNB, Scheme 7). As a source of hydrogen we used p-TosNHNH2 , which decomposes at heating giving diimide. The absence of vinyl-groups in the isolated polymer was established with 1 H-NMR spectroscopy (Fig. S3, S4).

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The change in the molecular weights during this reaction was insignificant (Table 1, Fig. S11) and it might be attributed to a conformational difference resulting in a change of polymer coils

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sizes between PVNB and H-PVNB. H-PVNB showed excellent solubility in chloroform and toluene (Table 2).

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H-PVNB

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Scheme 7. Hydrogenation of PVNB.

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Table 2 The solubility of polymers derived from PVNB. a

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Polymer CHCl3 CH2 Cl2 PVNB + + Cp-PVNB + O-PVNB + + S-PVNB + + H-PVNB + a The mark “+”, “–“ and “±” respectively.

THF PhCH3 DMSO DMF Et2 O n-heptane CH3 CN + + + + + ± + + + + mean that the polymer is soluble, insoluble and swelling,

3.2. Physico-chemical properties According to WAXD study the modified polymers are amorphous. Their WAXD patterns (excluding S-PVNB) are presented by two broad peaks with the peaks maxima of 2θ-angles close to PVNB. The values of d-spacing (4.7-4.8 Å and 10.1-10.2 Å), evaluated with WulfBragg equation, are close to each other for the studied polymers.

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Fig. 1. WAXD patterns for the modified polymers in comparison with the initial PVNB

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(1 – S-PVNB; 2 – O-PVNB; 3 – Cp-PVNB; 4 – H-PVNB; 5 – PVNB).

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The absence of crystallinity was also confirmed by DSC-analysis. There were no

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transitions that could correspond to melting polymers. Glass-transition temperatures (Tg) for the prepared polymers are very high (>250ºC) and were not observed with help of DSC till

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beginning the decomposition. By DMA analysis for S-PVNB we succeeded to show that Tg for this polymer is 277ºC.

The saturated main chains of polymers derived from PVNB provide them a high thermal stability. The temperature of 5 mass.% loss for polymers with hydrocarbonic substituents (PVNB, Cp-PVNB and H-PVNB) exceeds 360ºC in an inert atmosphere and 330ºC in air (Fig. 2). The main difference in the thermal behavior of Cp-PVNB or H-PVNB with PVNB is the absence of an increase in mass while heating in air. PVNB contains C-C double bonds in sidegroups, which are readily oxidized in air at 130-150ºC (Fig. 2, 3). At the same time, Cp-PVNB and H-PVNB are saturated compounds and cannot be as readily oxidized as PVNB.

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(b)

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(a)

Fig. 2. TGA curves for PVNB (1), Cp-PVNB (2) and H-PVNB (3) in argon (a) and in air (b). The modified polymers with polar side-groups (S-PVNB and O-PVNB) displayed a

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lower thermal stability (Fig. 3). For these polymers, the temperature of 5 mass.% loss was about

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320-330ºC in an inert atmosphere, while these values in air were 275 and 290ºC for S-PVNB and

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O-PVNB, correspondingly.

(a)

(b)

Fig. 3. TGA curves for PVNB (1), S-PVNB (2) and O-PVNB (3) in argon (a) and in air (b).

The porosity of the modified polymers was evaluated by the method of nitrogen lowtemperature adsorption/desorption. Nitrogen adsorption/desorption isotherms are presented in Fig. 4. Some of the obtained results are shown in Table 3.

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(a)

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(b) Fig. 4. Adsorption/desorption isotherms (a) for PVNB (1), Cp-PVNB (2) and H-PVNB (3) and (b) for PVNB (1), S-PVNB (2) and O-PVNB (3). Adsorption/desorption isotherms are of type IV according to the Brunauer classification, which indicates the occurrence of polymolecular adsorption and capillary condensation in mesopores. The type of hysteresis loop for all samples is H3, which indicates the slit shape of the mesopores. As can be seen from Table 3, the samples PVNB, Cp-PVNB and H-PVNB have high specific surface areas and pore volumes. These samples contain both meso and micropores. The

Journal Pre-proof volume of micropores increases in a range of PVNB, Cp-PVNB and H-PVNB. Moreover, according to calculations by the Horvat Kavazoe method, the predominant value of the width of the slot pore for these samples is 1 nm (Fig. 5a). BET surface areas and pore volume for the polymers with polar side groups (O-PVNB and S-PVNB) are noticeably lower than the corresponding

values

for

PVNB,

Cp-PVNB

or

H-PVNB.

Thus,

hydrogenation

and

cyclopropanation of PVNB lead to an increase in free volume in polymers (pore volume, Table 3), while epoxidation and thioacetylation make packing of polymer main chains more dense and the pore volume is decreased. Table 3 Porosity characteristics of polymers based on PVNB according to low temperature nitrogen adsorption/desorption method. Mesopore volume (ads), cm3 /g

Volume of micropores, cm3 /gc

0.50 0.67 0.62 0.38 0.32

0.15 0.20 0.18 <0.01 <0.01

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Specific Total Mesopore surface area Specific surface pore volume Polymer of 2 a area, m /g volume, (des), micropores, 3 cm /g cm3 /g m2 /gb PVNB 452 70 0.68 0.25 H-PVNB 382 96 0.79 0.61 Cp-PVNB 420 133 1.10 0.66 O-PVNB 56 0.38 0.18 S-PVNB 19 0.32 0.21 a – BET method; b – t-method; c - Dubinin–Radushkevich method.

al

Pore size distributions of mesopores for some polymers are presented in Fig. 5. As it can

rn

be seen from the shown dependencies, the samples have a narrow pore size distribution. The predominant size of mesopores is 4 nm.

Jo u

1 2 3

0,015

3

0,4

1 2 3

dV/dD, cm /g nm

0,5

0,3

3

dV/dD, cm /g nm

0,020

0,2

0,010

0,005

0,1 0,0

0,000 0,6

0,8

1,0

1,2

1,4

1,6

1,8

2

4

6

8

Pore width, nm

Pore width, nm

(a)

(b)

Fig. 5. Pore size distribution of micropores (a) and mesopores (b) for PVNB (1), CpPVNB (2) and H-PVNB (3). 3.3. Gas-transport properties

10

Journal Pre-proof Gas permeability (P) and diffusivity (D) coefficients of various gases (He, H2 , N 2 , O 2 , CO2 and CH4 ) in the polymers derived from PVNB were measured by Daynes-Barrer technique (Tables 4, 5). The corresponding solubility coefficients were determined as the ratio S = P/D (Table 6). The P values for gases decrease in the following order: P(CO 2 ) > P(H2 ) > P(He) > P(O 2 ) ≥ P(CH4 ) > P(N 2 ). Diffusion coefficients of gases in the prepared polynorbornenes change in order of increasing size of the gas molecule: D(O 2 ) > D(CO2 ) > D(N 2 ) > D(CH4 ) (Table 5). Solubility coefficients of carbon dioxide and methane, which are the most easily condensable gases among the considered gases, are the highest in all polymers derived from PVNB and the

f

order of solubility coefficients is as follows: S(CO 2 ) > S(CH4 ) > S(O 2 ) > S(N 2 ) (Table 6).

d, g/cm3

PVNB [47]

1.0414

15

H-PVNB Cp-PVNB

0.9836

19

1.0188

20

O-PVNB

1.2435

S-PVNB

1.1972

Permeability, Barrer

FFV, %a He

O2

N2

CO2

CH4

118

202

48

13

314

24

188

72

21

390

37

131

236

70

22

510

44

e-

pr

H2

Pr

Polymer

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Table 4 Gas permeability coefficients of various gases in polymers derived from PVNB.

310

9

45

67

7.6

3.8

119

7.1

12

18

14

1.3

0.59

33

1.5

rn

al

a – fractional free volume calculated by Askadskii method [50].

Hydrogenation or cyclopropanation of PVNB led to a noticeable increase in gas

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permeability (Table 4), while the incorporation of polar groups in side substituents (epoxidation and thioacetylation) resulted in lower gas permeability coefficients. This difference in the influence of a modification on gas permeability can be explained by the appearance of more bulky side substituents in the case of H-PVNB and Cp-PVNB and by the presence of dipoledipole interactions in O-PVNB or in S-PVNB. Thus, on the one hand, the introduction of bulky side-groups into polymers usually increases gas permeability, which is observed for H-PVNB and Cp-PVNB. On the other hand, the presence of polar groups within a polymer structure causes dipole-dipole interactions. These interactions bind molecules tightly and provide a denser packing of polymer main chains. As a result, the free volume content in O-PVNB and S-PVNB would be lower than it is in the PVNB, H-PVNB, and Cp-PVNB. It is consistent with the values of fractional free volume (FFV, Table 4) and the described above explorations of porosity using low-temperature adsorption/desorption method (Table 3). This explanation is also confirmed by the values of diffusivity coefficients (D) of gases in these polymers (Table 5). For H-PVNB and Cp-PVNB the D values are higher than for PVNB, while the values of solubility coefficients (S)

Journal Pre-proof of gasses in all these polymers are the same (Fig. 6 and 7, Table 6). In the case of O-PVNB and S-PVNB, the decrease in gas permeability is attributed to the drop of both D and S values (Tables 5 and 6, Fig. 6 and 7).

D(O2)polymer/D(O2)PVNB 2 1,5

f

1

oo

0,5

pr

0 H-PVNB

Cp-PVNB

O-PVNB

S-PVNB

e-

Fig. 6. Oxygen diffusivity coefficients of polymers derived from PVNB normalized to

Pr

the oxygen diffusivity coefficient of PVNB.

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0,8

rn

1,2

al

S(O2)polymer/S(O2)PVNB

0,4

0 H-PVNB

Cp-PVNB

O-PVNB

S-PVNB

Fig. 7. Oxygen solubility coefficients of polymers derived from PVNB normalized to the oxygen solubility coefficient of PVNB.

It is interesting that for O-PVNB the value of S(CO 2 ) is unexpectedly high. This value is even higher than the corresponding S value for much more permeable PVNB (Table 6), while the S values for all other gases are lower for O-PVNB than for PVNB. A possible reason of this observation could be the presence of polar C-O-bonds in O-PVNB. However, this effect has not been found for S-PVNB, which also contains polar bonds. Earlier the similar increase in S(CO 2 )

Journal Pre-proof was described for epoxidated metathesis polynorbornenes [2]. We assume that this unusual behavior of S(CO 2 ) for O-PVNB is rather explained by the specific interactions of CO 2 molecules with strained epoxide rings of side substituents in O-PVNB. Thus, it is possible to tune selectively the carbon dioxide permeability by incorporating epoxide rings into polymer structures. Table 5 Diffusivity coefficients of various gases in polymers derived from PVNB. Не 1700 2300 2200 1400 930

CH4 6.2 10 14 3.0 2.1

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PVNB [47] H-PVNB Cp-PVNB O-PVNB S-PVNB

Diffusion coefficient, ×10-8 cm2 /s H2 N2 O2 CO 2 830 15 40 31 1100 23 59 45 1100 31 70 57 500 11 18 9.1 270 7.6 9.1 8.5

f

Polymer

e-

al

PVNB [47] H-PVNB Cp-PVNB O-PVNB S-PVNB

Не 6.9 8.2 6.0 3.2 1.8

Solubility coefficient, ×10-4 cm3 /(cm3 ×cmHg) H2 N2 O2 CO 2 CH4 24 87 120 1000 380 28 91 120 760 370 21 71 100 900 310 13 35 42 1300 240 5.2 7.8 14 390 71

Pr

Polymer

pr

Table 6 Solubility coefficients of various gases in polymers derived from PVNB.

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Ideal selectivity of separations for the prepared polymers were evaluated as the ratio of pure gas permeability of each gas (α(A/B) = P A/PB). The modified polymers displayed attractive

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selectivity for separations of such pairs of gases as CO 2 /N2 , CO 2 /CH4 and H2 /N2 (Table 7). The highest values of these selectivities were obtained for O-PVNB and S-PVNB. Particularly striking is the CO 2 /N2 selectivity for S-PVNB. To increase CO 2 /N2 selectivity, usually C-Omoieties are incorporated. Herein we have found that the introduction of C(O)S-moieties also results in an enhancement of CO 2 /N2 selectivity and this approach can be used as a promising tool to tune properties of polymers when creating CO 2 -selective membranes. It is rather interesting that a well-known and traditional trade-off between selectivity and gas permeability is not found for the polymers derived from PVNB (Table 7). For instance, although PVNB, HPVNB and Cp-PVNB are more permeable than O-PVNB and S-PVNB, the O 2 /N2 selectivity is higher for PVNB, H-PVNB and Cp-PVNB. Table 7 Permeability selectivities for various pairs of gases for polymers derived from PVNB. Permeability selectivity Polymer O 2 /N 2 CO 2 /N2 CO2 /CH4 H2 /N2 H2 /CH4 He/CH4

Journal Pre-proof PVNB [47]

3.7

24

13.1

15.4

8.4

4.9

H-PVNB

3.4

16.2

9.2

14.8

8.4

5.1

Cp-PVNB

3.2

23.2

11.6

10.7

5.4

3.0

O-PVNB

2

31.3

16.8

17.6

9.4

6.3

S-PVNB

2.2

55.6

21.9

23.7

9.3

11.8

By applying the equations P = D·S and α(A/B) = PA/PB, we have factorized the ideal permeability selectivity in two different contributions α(A/B) = PA/PB = (DA/DB)·(SA/SB) = αD·αS (αD – a diffusivity selectivity contribution and αS – solubility selectivity contribution) (Tables S1

f

and S2). The largest diffusivity selectivity (αD) for the synthesized polymers are found for

oo

H2 /CH4 and He/CH4 pairs. This evidences that the contribution of αD to permeability selectivities for these pairs of gases is major. The same is true for O 2 /N 2 and H2 /N2 selectivities. At the same

pr

time, for pairs of gases containing CO 2 and/or CH4 the role of the solubility selectivity becomes more significant. For example, αS for CO 2 /N2 in the obtained polymers is always larger than αD

e-

and this indicates that the controlling factor is the solubility selectivity. The larger αS is rather

Pr

attributed to the increased solubility coefficients of CO 2 and CH4 due to an easier condensability of these gases among the tested ones and the affinity of these gases to the polymers prepared

al

(Tables 5, 6).

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4. Conclusions

The synthesis and gas-transport properties of polymers derived from addition poly(5-

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vinyl-2-norbornene) (PVNB) were described. Four different modifications of PVNB were successfully performed with a high degree of C-C-double bonds modifications (up to 99%). By functionalizing C-C-double bonds of PVNB, we succeeded to incorporate polar and non-polar moieties in the side-groups. The obtained polymers are amorphous and high Tg polymeric materials exhibiting a good thermal stability. The performed modifications exerted a dramatic influence

on

gas-transport

thioacetylation decreased

properties

of

resulting

gas permeability owing to

polymers.

While

the appearance

epoxidation

and

of polar groups,

cyclopropanation and hydrogenation led to an increase in the permeation of gases. At the same time, namely the epoxidized and thioacetylated polymers displayed attractive selectivities for the gas separation of such mixtures as CO 2 /N 2 , CO 2 /CH4 and H2 /N2 . The observed tendency to change in gas-permeability agrees well with results of porosity study by nitrogen lowtemperature adsorption/desorption method. Therefore, by performing these modifications, it is possible to tune gas-transport properties of materials based on addition poly(5-vinyl-2norbornene).

Journal Pre-proof Declaration of interests The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgement This work was supported by the Russian Science Foundation (project no. 17-19-01595). The determination of FFV values was carried out within the State Program of TIPS RAS.

oo

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Appendix A. Supplementary material

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Supplementary data to this article can be found online at …

Data availability

e-

The raw/processed data required to reproduce these findings cannot be shared at this time due to

Pr

technical or time limitations.

References

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Journal Pre-proof

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Graphical abstract

Journal Pre-proof Highlights 

Various functionalizations of addition poly(5-vinyl-2-norbornene) were performed.



The modifications were carried out in high yields without destruction of main chains.



Structure-property study of polynorbornenes for membrane gas separations.



Cyclopropanation and hydrogenation increase permeability with minimal decrease in

selectivity. 

Epoxidation or thioacetylation gave a substantial increase in CO 2 /N2 selectivity with

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decrease in permeability.