Spectroscopic Analysis of Binary Mixed-Solvent-Polyimide Precursor

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Spectroscopic Analysis of Binary Mixed-Solvent- Polyimide Precursor Systems with the Preferential Solvation Model for Determining Solute-Centric Kamlet-Taft Solvatochromic Parameters Alif Duereh, Yoshiyuki Sato, Richard Lee Smith, and Hiroshi Inomata J. Phys. Chem. B, Just Accepted Manuscript • DOI: 10.1021/acs.jpcb.5b07751 • Publication Date (Web): 26 Oct 2015 Downloaded from http://pubs.acs.org on November 2, 2015

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The Journal of Physical Chemistry

Spectroscopic Analysis of Binary Mixed-SolventPolyimide Precursor Systems with the Preferential Solvation Model for Determining Solute-Centric KamletTaft Solvatochromic Parameters Alif Duereh,† Yoshiyuki Sato,† Richard Lee Smith Jr†, ‡ and Hiroshi Inomata*†

†

Graduate School of Engineering, Research Center of Supercritical Fluid

Technology, Tohoku University, Aramaki Aza Aoba 6-6-11, Aoba-ku, Sendai 980-8579, Japan ‡

Graduate School of Environmental Studies, Research Center of Supercritical

Fluid Technology, Tohoku University, Aramaki Aza Aoba 6-6-11, Aoba-ku, Sendai 980-8579, Japan

*Corresponding Author Tel (Fax): +81-22-795-7282, e-mail: [email protected]

Keywords Cybotatic, preferential solvation model, specific interaction, UV-Vis spectroscopy

1 ACS Paragon Plus Environment


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Abstract Hydrogen bond donor/acceptor mixed-solvent systems for solutes that exhibit strong specific interactions are not readily characterized with methods that depend on solvatochromic parameters. In this work, the reaction of two monomers, 4,4’-oxidianiline (ODA) and pyromellitic dianhydride (PMDA), to form the common engineering plastic precursor, poly(amic acid) (PAA) are studied for the tetrahydrofuran (THF) mixed-solvent systems (THF-methanol, THF-ethanol, THF-water) with spectroscopy. Solute-centric (SC) Kamlet-Taft solvatochromic (K-T) parameters for the solvent environment around the monomer are determined using a proposed model that incorporates spectroscopicallydetermined local composition (XL) around the ODA monomer and the preferential solvation model. For the example reaction to occur under homogeneous conditions, mixed-solvent conditions need have HBA-rich local compositions (0.300.63) and low solute-centric acidity

( ) for obtaining homogeneous PAA precursor solutions. Regions of bulk composition that are HBD-rich ( > ) and HBD-poor ( ), favorable solute-centric Kamlet-Taft solvatochromic ∗ and and low ) compared with the respective NMP values allow parameters (high

preparation of homogeneous PAA solutions. Besides the local composition and solutecentric Kamlet-Taft solvatochromic parameters, the Hansen solubility parameter window of the monomer and polymer is important for estimating suitable compositions for preparing PAA solutions in mixed-solvent systems.

A mixed-solvent solubility parameter that is

outside of the solubility parameter window of the monomer and PAA polymer (Table 2) will probably not be suitable for forming and maintaining homogeneous PAA solutions. 4.4 Analysis of solvent effects In the preparation of engineering plastic precursors, there are a number of physical and chemical processes that occur depending on the monomer dissolution kinetics and the PAA formation kinetics in the mixed-solvent system. These physical and chemical processes are best discussed in phenomenological mechanistic steps noted in the literature24, 52,53 and in our previous work29 as shown in Figure 5. In a typical synthesis procedure, ODA monomer is dissolved in a mixed-solvent system and the solution is mixed with PMDA solid particles which initiates the reaction. The following mechanistic steps occur:

(i) Dissolution of ODA monomer occurs by specific interactions that require an HBArich local composition that has a solvent environment of high basicity ( > 0.48) and a solubility parameter window within 19-30 MPa0.5.


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(ii) Dispersion and dissolution of the PMDA monomer occurs that requires either an HBA-rich or HBD-rich local composition, except for the case of water due to hydrophobicity. (iii) Reaction and PAA gel formation around the PMDA particle occur due to ∗ crosslinking of PAA polymer that requires a solvent environment of high polarity ( >

0.63). (iv) Solvation of PAA polymer occurs via specific interactions that require an HBArich local composition that has a solvent environment of low acidity ( < 0.63), high ∗ basicity ( > 0.60), high polarity ( > 0.63), and a solubility parameter window within

21-29 MPa0.5 to support PAA growth in solution.

To form homogeneous solutions of PAA, the mixed-solvent composition must be chosen to provide favorable conditions for each phenomenological mechanistic step (Fig. 5) 4.5 Temporal variation of visible spectra Phenomenological mechanistic steps that occur when preparing homogeneous PAA solutions in binary mixed-solvent systems (Fig. 5) and in pure NMP as followed by temporal variation of the visible wavelength spectra and videos are summarized in Table 3 and in Figures S19-S21 (Section J). When pure NMP (HBA) is used as solvent (Table 3), the four phenomenological mechanistic steps for obtaining homogeneous PAA solutions are satisfied by the pure solvent system environment according to high HBA local composition, KamletTaft solvatochromic parameters, and Hansen solubility parameter. When binary mixedsolvent systems are used, there can be termination of the reaction process due to ODA monomer being insoluble in the solvent system (HBD-rich, A in Table 3, A in Fig. 5), PMDA being insoluble (B in Table 3, B in Fig. 5), excessive gelatinization (C in Table 3, C in Fig. 5) or PAA precipitation (D in Table 3, D in Fig. 5).



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Solvent conditions that are favorable for preparing homogeneous PAA solutions at high (2 or 5 wt%) concentration are shown in Table 3. For a given solvent system, solvent compositions that allow preparation of homogeneous PAA solutions have high dissolution and reaction rates compared with other solvent compositions. The reasons for the high dissolution rates and high reaction rates can be attributed to the HBA-rich local compositions and the solvent environment that has suitably high polarity and basicity and sufficiently low acidity values.

Both local composition (HBA-rich) and solvent environment (acidity,

basicity, polarity) and play important roles for preparing homogeneous PAA solutions. 4.6 Other polymer-mixed-solvent systems Several other polymer-mixed-solvent systems can be addressed.

For the polymer

mixed-solvent systems, polyethylene(terephthalate) (PET),54 poly(lactic acid) (PLA),55 polymethylsilsesquioxane (PMSQ)56 such as those used in electrospinning, homogeneous solutions are required. Compositions for preparing those polymer solutions18 have been based on Hansen solubility parameters in which the pure solvents of the mixed-solvent are unable to form homogeneous polymer solutions. Use of the local composition model and solute-centric Kamlet-Taft solvatochromic parameters developed in this work can allow one to estimate suitable composition ranges required and may help to optimize drying characteristics. 5. Conclusions In this work, a model was proposed to determine solute-centric Kamlet-Taft solvatochromic parameters for mixed-solvent systems that have solutes with strong specific interactions. The proposed model was developed from the spectroscopically-determined local composition around the central ODA (monomer) solute molecule, the preferential solvation theory and Kamlet-Taft solvatochromic parameters of the pure solvent and the transferable mixed-solvent complex HBA-HBD molecule Kamlet-Taft solvatochromic


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parameters. The solute-centric Kamlet-Taft solvatochromic parameters were found to be effective for analyzing the reaction conditions of three binary mixed-solvent systems that consisted of tetrahydrofuran with methanol, ethanol or water. The solute-centric Kamlet-Taft solvatochromic parameters were found to be similar to those of indicator-centric values, however, indicator-centric Kamlet-Taft solvatochromic parameters greatly overestimate mixed-solvent acidity. Favorable conditions for preparing homogeneous poly(amic acid) (PAA) solutions at high concentrations(5 wt%) were analyzed by local composition and solute-centric KamletTaft solvatochromic parameters. Phenomenological mechanistic steps were followed with the temporal variation of visible spectra and show that homogeneous PAA solutions are obtained when the dissolution rates of monomers and reaction rate of PAA polymer are high which is a direct result of the binary mixed-solvent system having HBA-rich local composition along with suitably high polarity and basicity values and sufficiently low acidity values.

The proposed procedure and model for determining solute-centric Kamlet-Taft

solvatochromic parameters are applicable to other solute-mixed-solvent systems that have strong specific interactions. 6. Abbreviations and symbols Abbreviations EtOH

ethanol

HBA

hydrogen-bond acceptor solvent (component 2)

HBD

hydrogen-bond donor solvent (component 1)

H2 O

water

K-T

Kamlet-Taft solvatochromic

MeOH

methanol

ODA

4,4’-oxidianiline monomer



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PAA

poly(amic acid) polymer

PMDA

pyromellitic dianhydride monomer

THF

tetrahydrofuran

Latin symbols f2/1

preferential solvation parameter, according to eq. (8)

f12/1


f12/2


K

weight fraction of solvent i

mole fraction of solvent i

Greek symbols

acidity Kamlet-Taft solvatochromic parameter

basicity Kamlet-Taft solvatochromic parameter

δ

Hansen solubility parameter

λ

maximum absorption wavelength of solute or indicator in units of nanometer (nm)

+

maximum absorption wavenumber of solute or indicator in units of kiloKaiser

∗

polarity Kamlet-Taft solvatochromic parameter

Superscript Bulk

bulk composition

L

local composition

Subscript 1

HBD solvent molecule, solvent type 1

2

HBA solvent molecule, solvent type 2

12

Complex HBD-HBA solvent molecule pair


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IC

indicator-centric Kamlet-Taft solvatochromic parameter

mixture

mixture property

pure

indicator-centric

Kamlet-Taft

solvatochromic

parameter

for the pure component SC

solute-centric Kamlet-Taft solvatochromic parameter

7. Acknowledgment Support from the Japanese government (MEXT) for a doctoral study scholarship (Alif Duereh) is gratefully acknowledged. 8. Supporting information Tables S1 to S8 and Figures S1 to S24 contain detailed experimental results, example of methodology for determining solute-centric Kamlet-Taft solvatochromic parameters, preferential solvation parameters, validation of 1-2 complex transferability among indicators and analyses of the poly(amic acid) precursors. This information is available free of charge via the Internet at http://pubs.acs.org/.

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Table 1. Fitting parameters ( f2/1, f12/1and + ) from the preferential solvation model (eq. 11) for mixed-solvent systems of hydrogen bond (HBA) acceptor solvent of tetrahydrofuran (THF, component 2), with hydrogen bond (HBD) donor solvents as methanol (MeOH), ethanol (EtOH), and water (H2O) for the 4,4’-oxidianiline (ODA) monomer as central solute molecule at 25 ºC. The + and + parameters are maximum absorption wavenumber of pure solvent components 1 and 2, respectively, in the unit of kiloKaiser (1kK=10,000/λmax (nm) =1000 cm-1) Solvent System (HBD (1)-HBA (2)) MeOH-THF EtOH -THF H2O-THF a

%ARD = ∑ N L

4OP QRST QRST

+ (kK) 40.40 40.25 40.98

f2/1 (-) 5.60 3.30 7.20

+ (kK) 39.43 39.43 39.43

f12/1 (-) 4.51 6.33 4.27

+ (kK) 40.40 39.66 39.55

%ARDa

R2 b

0.013 0.029 0.074

0.999 0.995 0.993

N, where +UV# is maximum absorption wavenumber (kK) calculated

from eq. (11) and +G is the experimental maximum absorption wavenumber (kK). b 2

R =Coefficient of determination.

c

N=number of experimental data.


Nc 11 11 12

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Table 2. Experimental results for preparation of homogeneous (○) and heterogeneous (×) poly (amic acid) (PAA) solutions of 5 wt % synthesized from 4, 4’-oxidianiline (ODA) and pyromellitic dianhydride (PMDA) monomersa in weight (W) and mole (X) fractions for tetrahydrofuran (THF, component 2) with methanol (MeOH), ethanol (EtOH), water (H2O) at 25 ºC. Solute-centric Kamlet-Taft solvatochromic parameters were calculated with eqs. (1)(3).

Local compositions around the ODA monomer were calculated from eqs. (4)-(6).

Hansen solubility parameters (δ) of mixed-solvents were estimated from volume fraction average of the pure solvent values. Solute-centric δ 0.5 (MPa ) K-T parameters Phase ∗ 1.0 1.00 0 1.00 0 0 0.58 0.62 THF × 19.5 0.9 0.80 0.01 0.82 0.17 0.14 0.61 0.63 × 20.6 0.8 0.64 0.04 0.66 0.30 0.27 0.63 0.64 ○ 21.7 0.7 0.51 0.09 0.51 0.40 0.40 0.65 0.65 ○ 22.8 0.6 0.40 0.15 0.38 0.46 0.52 0.67 0.66 ○ 23.8 0.5 0.31 0.24 0.27 0.49 0.63 0.69 0.67 ○ 24.8 0.4 0.23 0.35 0.17 0.47 0.73 0.70 0.67 × 25.8 0.3 0.16 0.49 0.10 0.42 0.83 0.70 0.68 × 26.8 0 0 1.00 0 0 1.06 0.69 0.68 MeOH × 29.6 0.9 0.85 0.00 0.87 0.12 0.10 0.59 0.62 EtOH-THF × 20.3 0.8 0.72 0.03 0.56 0.42 0.20 0.60 0.63 ○ 21.0 0.7 0.60 0.06 0.41 0.53 0.31 0.62 0.64 ○ 21.8 0.6 0.49 0.10 0.30 0.60 0.41 0.64 0.65 ○ 22.5 0.5 0.39 0.16 0.21 0.63 0.52 0.66 0.65 ○ 23.2 0.4 0.30 0.23 0.14 0.63 0.62 0.68 0.65 × 23.9 0.3 0.21 0.34 0.08 0.58 0.71 0.70 0.64 × 24.6 0.90 0.78 0.61 0 0 1.00 0 0 EtOH × 26.5 0.98 0.93 0 0.94 0.06 0.03 0.58 0.62 19.9 H2O-THF × 0.95 0.83 0.01 0.85 0.14 0.08 0.59 0.63 20.7 ○ 0.9 0.69 0.03 0.72 0.26 0.17 0.60 0.65 22.0 ○ 0.8 0.50 0.09 0.50 0.41 0.32 0.61 0.70 24.6 ○ 0.7 0.37 0.18 0.35 0.47 0.46 0.61 0.74 27.2 ○ 0.6 0.27 0.29 0.22 0.49 0.60 0.60 0.80 30.1 × 0.5 0.20 0.40 0.14 0.46 0.71 0.59 0.85 32.7 × 0 0 1.00 0 0 1.17 0.47 1.09 47.8 H2 O × a 0.5 0.5 0.5 0.5 δwindow=21-29 MPa ; δODA=21 MPa ; δPMDA=24.5 MPa ; δ PAA=22.1 MPa [29]. Solvent system (HBD-HBA)

K W0XY

W0XY

Local composition



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48

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Table 3. Solvent systems and phenomenological mechanistic steps as followed by visible spectra (410 nm) when preparing homogeneous poly(amic acid) (PAA) precursors for engineering plastics with binary mixed-solvents of tetrahydrofuran (THF, component 2) with methanol (MeOH), ethanol (EtOH), water (H2O) at 25 ºC according to Hansen solubility parameters (δ), solute-centric Kamlet-Taft solvatochromic (K-T) ∗ parameters ( , , ), and local composition. Green-shaded rows indicate favorable conditions for preparing homogeneous 5 wt% PAA solutions. Solvent system W0XY Local composition (HBD-HBA) THF 1.0 0 1 0.01 0.82 0.80 0.09 0.51 0.51 0.35 0.17 0.23c 1 0 MeOH 0 0 1 THF 1.0 0.00 0.87 0.85 0.06 0.41 0.60 0.23 0.14 0.30 1 0 EtOH 0 0 1 THF 1.0 0 0.94 0.93 0.69 0.03 0.72 0.20 0.40 0.14 1 0 H2O 0 NMP 1 0 1

δ Solute-centric K-T parameters (MPa0.5) ∗ 0 0.58 0.62 19.5 0.14 0.61 0.63 21.7 0.27 0.63 0.64 22.8 0.73 0.70 0.67 25.8 1.06 0.69 0.68 29.6 0 0.58 0.62 19.5 0.10 0.59 0.62 20.3 0.31 0.62 0.64 21.8 0.62 0.68 0.65 24.6 0.90 0.78 0.61 26.5 19.5 0 0.58 0.62 0.03 0.58 0.62 19.9 0.17 0.60 0.65 22.0 0.71 0.59 0.85 32.7 1.17 0.47 1.09 47.8 0 0.72 0.95 22.9

Phenomenological mechanistic stepsa and barriers (A, B, C, D)b ---C (low δ and ) ∗ ---D (low ) ----Homogeneous ----Homogeneous -A (non-specific interactions) ---C (low δ and ) ∗ ---D (low Z[ ) ----Homogeneous ---D (high Z[ and HBA-poor) -A (non-specific interactions) ---C (low δ and ) ∗ ---D (low ) ----Homogeneous --- D (high and HBA-poor) -A and B (non-specific interactions) ----Homogeneous

Note: a=ODA dissolution; =PMDA dispersion and dissolution; =Surface reaction, PAA gel formation; =PAA solvation and growth b A=ODA insolubility; B=PMDA insolubility; C=Excessive gelatinization; D=PAA precipitation. c Only confirmed at 2 wt% PAA. 34

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a)

Specific Interaction

HBA-HBD Complex molecule

HBD molecule

Cybotactic Region

b)

Specific Interaction

HBA-HBD Complex molecule

HBA molecule

Cybotactic Region

Figure 1.

Cybotatic regions of (a) solvatochromic indicator (indicator-centric) and (b)

monomer (solute-centric) in a solvent mixture showing specific interactions (dashed-lines) of hydrogen-bond donor (HBD) molecules (solvent type 1), hydrogen-bond acceptor (HBA) molecules (solvent type 1), and HBA-HBD complex molecules (solvent type 1-solvent type 2). The solvatochromic indicator (a) is 2,6-diphenyl-4-(2,4,6-triphenyl-1-pyridinio) phenolate or Reichardt's dye and the monomer (b) is 4, 4’-oxidianiline (ODA). 35 ACS Paragon Plus Environment


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Solute-centric steps

Choose solvent system

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Indicator-centric steps

Monomer as central solute molecule

Indicator as central solute molecule

Measure λmax shift for full range of compositions (λmax = f (XBulk))

Measure λmax shift for full range of compositions (π*, β, α = f (XBulk))

Apply preferential solvation model to fit f2/1, f12/1, and + parameters from spectral data

Apply preferential solvation model to ∗ fit , , and parameters

Calculate local compositions ( , , ) around solute

Optionally calculate local compositions around indicator (not used)

Local composition around solute ) ( , ,

Solute-centric K-T parameters ∗ ∗ ∗ ∗ = + +

Complex molecule K-T parameters ∗ , , ) (

= + + = + +

Figure 2. Procedure for determining solute-centric Kamlet-Taft solvatochromic parameters with the model, eqs. (1)-(3) for an arbitrary mixed-solvent system.


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Figure 3. Local mole fractions, (HBD solvent), (HBA solvent), and (complex

molecule HBD-HBA solvent) around central solute molecule, 4, 4’-oxidianiline (ODA) for solvent systems, (a) methanol, (b) ethanol, and (c) water with tetrahydrofuran (THF) at 25 ºC. Local composition that has higher than is HBA rich. Homogeneous poly(amic acid) (PAA) regions (green-shaded area) are defined by polymerization experiments (Table 2). 37 ACS Paragon Plus Environment


\]^

a)

_]^

b)

c)

`∗]^

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Figure 4. Solute-centric Kamlet-Taft solvatochromic parameters of the methanoltetrahydrofuran (solid-black lines), ethanol-tetrahydrofuran (dotted dashed-red lines) and water-tetrahydrofuran (dashed-blue lines) mixtures at 25 ºC: (a) solute-centric acidity ( ); ∗ (b) solute-centric basicity ( ); and (c) solute-centric polarity ( ).


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Barriers

Mechanistic steps Local composition


A. ODA insolubility

ODA dissolution

B. PMDA insolubility

C. Excessive gelatinization

Surface reaction,

PMDA dispersion and dissolution

D. PAA Precipitation

PAA solvation and growth

PAA gel formation - HBA-rich

- Acidity ( < 0.80)

Solvent - Basicity ( > 0.48) environment ∗

- Polarity ( > 0.47)

- HBA-rich

- HBA-rich or HBD-rich

- < 1.0

- < 0.80

- > 0.30 -

∗

- > 0.48

> 0.50

-

∗

> 0.63

- HBA-rich

- < 0.63 - > 0.60

∗ - > 0.63

Figure 5. Mixed-solvent conditions for preparing homogeneous poly(amic acid) (PAA) precursors considering by local composition and solute-

∗ centric Kamlet-Taft solvatochromic parameters ( , , ) according to the phenomenological mechanistic steps. Solvent mixtures should

have a Hansen solubility parameters (δ) of 21-29 MPa0.5 to obtain homogeneous PAA solutions at 25 ºC. 39

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For Table of Contents Use only: Spectroscopic Analysis of Binary Mixed-Solvent-Polyimide Precursor Systems with the Preferential Solvation Model for Determining SoluteCentric Kamlet-Taft Solvatochromic Parameters Alif Duereh,† Yoshiyuki Sato,† Richard Lee Smith Jr†, ‡ and Hiroshi Inomata*†


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Spectroscopic Analysis of Binary Mixed-Solvent-Polyimide Precursor

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