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Radical (Co)polymerization Kinetics Obtained From Droplet-Based Microfluidics

December 04, 2014

Emmanuel MIGNARD Patrick MAESTRO

®CNRS / UMR5258 LOF

Atelier de Prospective du GFP - Intensification des procédés liés aux polymères

Miniaturized tools - Process & Analysis

Introduction

Concept of droplet-based microfluidics for chemistry

Coupling inline analytical tools

Polymerization reactions within droplets

Methodology

Polymerization of acrylic acid

Copolymerization of acrylic acid with Sodium Styrene sulfonate

Conclusion and outlooks

July 16, 2009 EPF’09 - European Polymer Congress 2009 - Graz, Austria

Outline


Introduction




Methodology




2

?

Radical Copolymerization Kinetics Obtained From Droplet-Based Microfluidics

• Microfluidics

The science and technology of systems capable to handle fluids, and where at least one of their characteristic dimensions is of the micrometer

3

At small length scales, transport phenomena can be precisely controlled:

Mixing - Thermal transfers - Concentrations - Flows

≤ mm

Radical Copolymerization Kinetics Obtained From Droplet-Based Microfluidics

Size of the reactor

Mass & heat transfer

4

10 - 60 ms Mixing time

> h > h 1 h 30 s Residence time

- 6 mL/h 2 mL/h 0.1 mL/h

10 1500 3000 30000 Surface/Volume

3 L 3 µL 0.3 µL 0.3 nL

Flow-rates

19 cm 1 mm 500 µm 50 µm

batch milli micro

0.4 - 1.5 s 3 -10 s 6 s

exothermic

fast

slow

sampling

Reactions

++ + - -

- + ++ ++

- - + ++

++ ++ - ++

Lab Tools: Droplet-Based Microfluidics

Importance of the size of the microreactor

5

Microfluidics : a miniaturized continuous approach

Droplets = independent chemical microreactors

Control of flows/mixing Control of concentrations Compartmentalization Control of residence times Mixing inside by wall forced convection Management of viscosity issues Very high S/V ratio Favors heat exchange Temporal resolution Time/space correspondence Small volumes Improve safety, less waste

Sarrazin et al. 2006

A

B

Oil

Oil

Droplet-Based Microfluidics

6

Analysis = inline monitoring in ‘real time’ by using non-intrusive techniques

Transparency Microscope, spectroscopy, IR Thermography Sequential production Potential for High Throughput Experiments

50 µm

Ideal tool for kinetic data acquisition

Low cost & user-friendly Droplet-Based Micro- or Millifliduics

• “Same” microreactors, hydrodynamic properties and possible “inline” analysis

High S/V ratio, space/time correspondence, …

• Higher residence times (about hours)

• Good chemical resistance (PTFE, glass, …)

• Large choice of commercial tubing, capillaries and connectors

• No need of a cleanroom nor expensive microfabrication machines

Tubing FEP 1/8’’OD & 1/16”ID

Droplet-Based Microfluidics

7

• Raman (back scattering)

– Identification

– Conversions

• Thermal Infra-Red CCD

– Heat of reaction

• Spectroscopy UV-Vis

– Turbidity (frequency of droplets)

– Absorption

Tube FEP 1/8’

Cylindre chauffant

Passage du laser

Tube FEP 1/8’

Cylindre chauffant

Passage du laser Probe Heating device


8

1000 2000 3000

-200

-100

0

100

200 0

0.5

1

Mixing by Raman imaging

(false colors)

• OceanOptics Laser: 532nm, 500mW

• InPhotonics probe

– Optical fiber: polyurethane, length: 5m, Ø: 200µm

– Material: stainless steel and quartz

– Backscattering

– Focus distance: about 7,5mm

• OceanOptics QE65000 Spectrometer

– Resolution: 18cm-1

– Software: SpectraSuite

– USB

• Possible sample holder

For a qualitative determination

$


9

• Laser NdYAG

– 632 nm, 500mW

– Doubled frequency

• Olympus BXFM Microscope:

– Objectives: x10 ; x50 ou 100x

– Backscattering

• Jobin-Yon LABRAM HR800 Spectrometer

– Resolution: 1 cm-1

– Software: Labspec

• Motor drive control of x-y-z table

• Possible sample holder

In depth quantitative analysis by Raman spectroscopy

$$$


10


Introduction




Methodology




July 16, 2009 EPF’09 - European Polymer Congress 2009 - Graz, Austria

Outline


Introduction




Methodology




11

Monitoring of acrylic acid polymerization

12

Experimental set-up

Fluorous oil

Aqueous phase

Generation of droplets

0

2000

4000

6000

8000

10000

12000

1600 1640 1680 1720 1760 1800

Raman shift (cm-1)

inte

ns

ité

solution 3

solution 5

solution 7

solution 9

solution 10

0

2000

4000

6000

8000

10000

12000

1600 1640 1680 1720 1760 1800

Raman shift (cm-1)

inte

ns

ité

solution 3

solution 5

solution 7

solution 9

solution 10

Calibration @ 1640 cm-1

and @ high temperature

Concentration of AA (%)

Ram

an s

catt

erin

g

Calibration based on Raman spectroscopy


Experimental set-up

13

C:\Documents and Settings\nlorber\Mes documents\DOC Thèse\PAA\Tufu cylindrique\09NLR1112-03 PAA40%R200T80°C\t0.txt

1580 1590 1600 1610 1620 1630 1640 1650 1660 1670

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Ab

sorb

ance

Un

its

Seite 1 von 1


1580 1590 1600 1610 1620 1630 1640 1650 1660 1670

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015

00

020

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025

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Ab

sorb

ance

Un

its

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ance

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sorb

ance

Un

its

Seite 1 von 1 0

5000

1 104

1.5 104

2 104

2.5 104

1600 1620 1640 1660 1680 1700

Cou

nts

Raman shift (cm-1

)

0

0.2

0.4

0.6

0.8

1

0 50 100 150 200 250 300 350

Conve

rsio

n

Time (s)



1580 1590 1600 1610 1620 1630 1640 1650 1660 1670

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1 residence time

1 position Monomer conversion with time

1 information 14


Droplets allow using the time vs space correspondence


Kinetics

15 Macromolecules, 43 (2010) 5524

Macromolecular Symposia, 296 (2010) 203

**

OOH

n

OH

O

Na2S2O8

H2O,

pH = 2.5

n

1

1

1

1

1050

0

1640

0

1050

1640

0,

,

0,

,11

cm

cm

cm

t

cm

t

m

tm

m

tm

I

I

I

I

C

C

n

n

Conversion:

[AA]0 = 2.8 mol.L-1 (20 wt. %) pH = 1.8 ; 81 °C

0

0.2

0.4

0.6

0.8

1

0 50 100 150 200 250 300 350

[AA]/[I]=225

[AA]/[I]=100

[AA]/[I]=50

[AA]/[I]=25

Con

ve

rsio

n

Temps (s)

y = 1-((((1/3*(M0-m1)*m2)+(2...

ErrorValue

2.01655.6997m1

0.000306380.0069945m2

NA0.0078702Chisq

NA0.99057R2

y = 1-((((1/3*(M0-m1)*m2)+(2...

ErrorValue

1.1124.914m1

0.000386720.01166m2

NA0.0034263Chisq

NA0.99489R2

y = 1-((((1/3*(M0-m1)*m2)+(2...

ErrorValue

0.723997.3965m1

0.000611010.019224m2

NA0.0039064Chisq

NA0.99532R2

y = 1-((((1/3*(M0-m1)*m2)+(2...

ErrorValue

0.653517.2875m1

0.00117060.028942m2

NA0.0053381Chisq

NA0.99328R2

0,0125

0,028

0,056

0,112

Time (s)

[ I2 ]0 (mol.L-1)

-5

-4.5

-4

-3.5

-3

-2.5

-2

-5 -4 -3 -2 -1 0 1 2

y = -4.9841 + 1.3441x R2= 0.98648

y = -1.8318 + 0.5156x R2= 0.99441

ln R

p,0

ln [NaPS]0 ou ln [AA]

0

Polymerization rate:

[AA]k

Ifkk

dt

AAdR

t

d

pp 02


[AA]0 = 2.8 mol.L-1 (20 wt. %) pH = 1.8 ; [I2]0 = 0.028 mol.L-1

0

0,2

0,4

0,6

0,8

1

0 100 200 300 400 500 600 700

68°C

74°C

81°C

86°C

90°C

Conve

rsio

n

Temps (s)Time (s)

T °C

16

Kinetics **

OOH

n

OH

O

Na2S2O8

H2O,

pH = 2.5

n

1

1

1

1

1050

0

1640

0

1050

1640

0,

,

0,

,11

cm

cm

cm

t

cm

t

m

tm

m

tm

I

I

I

I

C

C

n

n

Conversion:

Macromolecules, 43 (2010) 5524

Macromolecular Symposia, 296 (2010) 203

Overall activation energy of the poly rate:

-5

-4.5

-4

-3.5

-3

-2.5

-2

-1.5

2.7 2.75 2.8 2.85 2.9 2.95

Ln Rp,0 (40%)

Ln Rp,0 (20%)

y = 25.399 - 9.8893x R2= 0.99568

y = 23.414 - 9.5637x R2= 0.9868

Ln

Rp

,0

1/T x 103 (°K

-1)

Ea = 82 kJ.mol-1

Ea = 80 kJ.mol-1

RT

EAR a

p, ln)ln( 0

Water

Monitoring of the copolymerization

17

Internal reference

Raw Raman spectra from monomers

Water spectra in the

interest area (zoom)

Smooth

1. Baseline 2. Deconvolution 3. Calibration 4. Test 5. Validation


Corrected Raman spectra from monomers 1. Baseline 2. Deconvolution 3. Calibration 4. Test 5. Validation

Intensity (area) is proportional to the concentration 18


Validation of the calibration 1. Baseline 2. Deconvolution 3. Calibration 4. Test 5. Validation

19

1597-1602 cm-1 1628-1633 cm-1


Validation of the calibration 1. Baseline 2. Deconvolution 3. Calibration 4. Test 5. Validation

20

1. Baseline 2. Deconvolution 3. Calibration 4. Test 5. Validation

Temperature 23 °C 70 °C 80 °C

SSNa

1597-1602 cm-1

3,21 ±0,02 3,68 ±0,06 3,6 ±0,06

1628-1633 cm-1

3,27 ±0,02 3,67 ±0,06 3,53 ±0,05

AA 2,01 ±0,06 1,65 ±0,03 1,61 ±0,05

P(NaSS) 0,71 ±0,01 0,84 ±0,03 0,8 ±0,02

n (cm-1)

AA + NaSS

NaSS+ P(NaSS)

AA

Simulations with model solutions


21

Assume terminal model of copolymerization:

−𝑑 𝑀1

𝑑𝑡= 𝑘11 𝑀1

∗ 𝑀1 + 𝑘21 𝑀2∗ 𝑀1

−𝑑 𝑀2

𝑑𝑡= 𝑘12 𝑀1

∗ 𝑀2 + 𝑘22 𝑀2∗ 𝑀2

--M1* + M1 ---M1

*

--M2

* + M1 ---M1*

--M1

* + M2 ---M2*

--M2

* + M2 ---M2*

k11

k21

k12

k22

−𝑑 𝑀1

𝑑 𝑀2=

𝑀1 𝑟1 𝑀1 + 𝑀2

𝑀2 𝑀1 + 𝑟2 𝑀2

𝑟1 =𝑘11

𝑘12 et 𝑟2 =

𝑘22

𝑘21


22 Time (s) Time (s)

• [AA]0 = 2.8 mol.L-1 (20 wt. %) ; pH = 1.8 ; 70 °C

• AA / NaSS = 80 / 20 (wt. % ratio)


23

-0,25

-0,2

-0,15

-0,1

-0,05

0

0,05

-2

0

2

4

6

8

10

0,02 0,04 0,06 0,08 0,1 0,12 0,14

Data 1A C

F(f

-1)/

f

F²/f

-2

0

2

4

6

8

10

0 1 2 3 4 5 6 7 8

Data 35

12

y = -0,78845 + 1,2798x R2= 0,99964

y = -1,3804 + 0,89305x R2= 0,99615

F(f-1

)/f

-0,4

-0,3

-0,2

-0,1

0

0,1

0 0,05 0,1 0,15 0,2 0,25

Data 2

B

η

ξ

Drift in composition with residence time

𝑟𝐴𝐴 =𝑘11𝑘12

𝑟𝑆𝑆𝑁𝑎 =𝑘22𝑘21

Droplet-based microfluidics 0.26 2.10

Wiley et al. (1958) 0. 2 4.5

Grabiel et Decker (1962) 0.1 1.0

Kelen-Tüdos Fineman-Ross

Time - NaSS - AA

Molecular weights with residence time by off-line SEC


24

Continuous synthesis of (co)polymers within droplets in a wide range of conditions

Reaction monitoring by Raman confocal microspectrometry

Straightforward data acquisition platform

No manual handling of samples

Data non-accessible in ‘conventional’ batch reactors

Better heat transfer allows performing fast/exothermic reactions

Thank you for your attention! Thanks to

CNRS LOF: Dr. Nicolas Lorber Ousmane Savané Daniel Subervie

Solvay LOF: Dr. Pierre Guillot Dr. Flavie Sarrazin Solvay RIC-Paris: Dr. James Wilson IPREM – UPPA: Dr. Oihan Garagalza Dr. Bruno Grassl Dr. Stéphanie Reynaud

Bordeaux

December 04, 2014 Atelier de Prospective du GFP - Intensification des procédés liés aux polymères