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1

Monitoring Interlayer Monitoring Interlayer Formation by Infrared Formation by Infrared

Spectroscopy in Layered Spectroscopy in Layered Reactive Polymer BlendsReactive Polymer Blends

J. Lia,b, M. Prustya,c, H. Goossensa,c

a Eindhoven University of Technology - Department of Chemical Engineering and Chemistry- Laboratory of Polymer Technology

P.O. Box 513, 5600 MB Eindhoven, The Netherlands b Fudan University -Department of Macromolecular Science,

200433 Shanghai, Chinac Dutch Polymer Institute, P.O. Box 902, 5600 AX Eindhoven, The

Netherlands


2

OutlineOutline

Introduction

Objective

Modification of SAN in solution

On-line Monitoring interlayer reaction by ATR-FTIR in layered reactive polymer blends

Future work


3

IntroductionIntroduction

Polymer blends : Combination of existing polymers

Advantage:

Cheap

Tuning properties easily

high property/cost performances

C. Koning, Prog. Pol. Sci (1998), 707

Disadvanatage:

Immiscibility

Coarse phase morphology


4

In situ compatibilization by reactive blendingA/B immiscible blend A B

B - YA/B

X-functionalized A*

X-functionalized C* (miscible with A)

+“in situ”

block or grafted copolymersY-functionalized B*

Y-functionalized D* (miscible with B)


5

IntroductionIntroductionReactive blending:


Reactive additive for phase (A)

Reactive additive for phase (B)

In situ generated copolymer

X’Y’

(A)-branch-(B)

XY

(A)-graft-(B)

X

Y

X’Y’


6

Objective

Understand the reactive blending process from a fundamental point of view

---- the competition between processes like diffusion to interface and reaction between the components inside the interface


7

OxazolineOxazoline:: Universal Universal ccompatibilizerompatibilizer

B.M. Culberston, Prog. Pol. Sci (2002), 579

O N

R'

RX R'CONCH2CH2X

R

RCOOHR'CONHCH2CH2OOCR

RCOSH

R'CONHCH2CH2SOCR

ROH

R'CONHCH2CH2OR

RCOCl

R'CONOCR

CH2CH2Cl

RNH2

R'CONHCH 2CH 2NHR


8

Modification of SAN in solutionModification of SAN in solutionNH2

OH

AE

N

N

O N

SAN

SAN-oxazoline

+

Reaction scheme

N

O

NH

CH2

CH2

O

O

Polymer

Polymer-COOH+


9

Polymer modification

Materials: SAN, AE, catalyst, DCB (solvent)

Procedure: Precipitation: 5 wt% of polymer in chloroform and

then add to it 10 times methanol Drying: 48 hrs. at 45 °C

Parameters: Ratio AN/AE, different catalysts, catalyst

concentration, temperature and reaction time.


10

Characterization (Mid-IR)

1710 1700 1690 1680 1670 1660 1650 1640 1630 1620

-0.05

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60

0.65

0.70

abso

rban

ce

wavenumber (cm-1)

SAN 1hr 2hrs 3hrs 4hrs 6hrs 8hrs

2400 2200 2000 1800 1600 1400

-0.2

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

abso

rban

ce

wavenumber (cm-1)

SAN SAN-oxa

Nitrile

Oxazoline

Phenyl


11

Kinetics of solution modificationoxa( 1:1, 2%)

0

0.002

0.004

0.006

0.008

0.01

0.012

0 2 4 6 8 10

time(hrs)

oxa

(mm

ol)

130 °C

140 °C

150 °C

160 °C

K = 6.4*104exp(-10.2*103/T) ( g/mmol·min)


12

oxa(1:1,4% cat)

0

0.002

0.004

0.006

0.008

0.01

0.012

0 2 4 6 8 10

time(hrs)

oxa

(mm

ol) 130 deg

140 deg

150 deg

160 deg

oxa(1:4,2% cat)

0

0.005

0.01

0.015

0.02

0.025

0 2 4 6 8 10

tim e(hrs)

ox

a(m

mo

l) 130 deg

140 deg

150 deg

160 deg

oxa(1:4,4%cat)

0

0.005

0.01

0.015

0.02

0.025

0.03

0 5 10

time(hrs)

oxa(m

mo

l) 130 deg

140 deg

150 deg

160 deg

oxa( 1:1, 2% cat)

0

0.002

0.004

0.006

0.008

0.01

0.012

0 2 4 6 8 10

time(hrs)

oxa

(mm

ol)

130 °C

140 °C

150 °C

160 °C


13

Materials: SAN-oxazoline (1.9 ~5.4 wt% oxazoline)

poly (ethylene-co-methacrylic acid) (15 wt% acid)

Sample:

a: thin film of SAN-oxazoline (100nm~ 400nm) b: thick film of PE-co-MA (~ 0.5mm)

On-line monitoring of interfacial On-line monitoring of interfacial reaction reaction by ATR-FTIRby ATR-FTIR

a

b


14

Instrumental set-up

d=1~2 µm

IR radiation

detector

evanescent wave

dd

IREIR radiation

detector

evanescent wave

dd

IRE

400nm


15

O

NP C

O

OH + P'

nP C

O

ON C

n

O

P'

ResultsResults

120 oC

190 oC

5.4 wt% oxazoline

400nm SAN-oxa layer

1850 1800 1750 1700 1650 1600 1550 1500 1450

0.00

0.01

0.02

0.03

0.04

0.05

0.06

0.07

Wavenumber (cm-1)

ab

so

rba

nce

0min 10min 20min 30min 60min 90min 117min

Ester

OxazolineAmide I

Amide II


16

Difference Spectroscopy

1760 1740 1720 1700 1680 1660 1640 1620-0.020

-0.015

-0.010

-0.005

0.000

0.005

0.010

0.015

0.020

0.025

0.030

0.035

ab

so

rba

nce

wavenumber (cm-1)

Ester Amide I

Oxazoline


17

Intensity Vs. Time

20 40 60 80 100 120 140 160-0.15

-0.10

-0.05

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

inte

nsi

ty [a

.u.]

time [min]

oxazoline amide I amideII ester


18

Mirror image

overlapping

20 40 60 80 100 120 140 160-0.15

-0.10

-0.05

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

inte

nsity

[a.u

.]

time [min]


origianl

original After reversal

20 40 60 80 100 120 140 160

0.0

0.1

0.2

0.3

0.4

0.5

0.6

inte

nsi

ty/a

.u.

time/min

oxazolineamide I amideII ester

20 40 60 80 100 120 140 160

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

inte

nsi

ty/a

.u.

time/min



19

Effect of temperatures

-20 0 20 40 60 80 100 120-0.05

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

inte

nsi

ty [a

.u.]

time [min]

150 oC

160 oC

170 oC

180 oC

190 oC

200 oC

Equilibrium ?

Diffusion limitation

?


20

Step annealing І:

190 oC ~170 oC

Equilibrium ?

-20 0 20 40 60 80 100 120 140 160

0.0

0.1

0.2

0.3

0.4

0.5

inte

nsi

ty [a

.u.]

time [min]

190 oC 2hrs to 170 oC 0.5 hr

190 oC 2hrs


21

-20 0 20 40 60 80 100 120 140 160 180 200 220 240 260 280

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7in

tens

ity [a

.u.]

time [min]

190 oC

150 oC 3hrs to 190 oC 1hr



Step annealing II:

150 oC/160 oC/170 oC ~ 190 oC


22

Step annealing II:

　 SlopeSlope in curve

of 190oC

150oC ~ 190oC 0.00707 0.00679

160oC ~ 190oC 0.00329 0.00405

170oC ~ 190oC 0.00148 0.00141

150 oC/160 oC/170 oC ~ 190 oC

-20 0 20 40 60 80 100 120 140 160 180 200 220 240 260 280

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

inte

nsity

[a.u

.]

time [min]

190 oC





23

Effect of content of oxazoline

-20 0 20 40 60 80 100 120 140 160

0.0

0.1

0.2

0.3

0.4

0.5

inte

nsity

[a.u

.]

time [min]

1.9% 3.45% 5.4%

Temp. =190 oC

　 3.45/1.9 5.4/1.9

ratio of oxazoline's content

1.815789

2.842105

ratio of amide I's intensity

1.974067

2.91471

-0.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0-0.002

0.000

0.002

0.004

0.006

0.008

0.010

0.012

0.014

0.016

0.018

0.020

0.022

initi

al s

lope

content of oxazoline (%)

slope


24

Effect of thickness of SAN-oxazoline layer

0 20 40 60 80 100 1200.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45In

ten

sity

[a

.u.]

time [min]

100nm 400nm

Temp. =190 oC


25

Solution mixture of SAN and SAN-oxa

0 20 40 60 80 100 120 140

0.0

0.1

0.2

0.3

0.4

inte

nsity

[a

.u.]

time [min]

1.9% 5.4% mixture, 1.9%

Temp. =190 oC


26

ConclusionsConclusionsATR-FTIR can be used to monitor the

interfacial reaction between oxazoline and acid groups and follow the kinetics.

There is no side reaction in the system. It’s not an equilibrium reaction. low temperature – higher diffusion

limitation and vice versa. The thickness of SAN-oxa layer and the

position of the oxazoline group in SAN is not important for the reaction.


27

Future WorkFuture Work

ATR-FTIR: do quantitative analysis on the data

Ellipsometry: follow the interlayer formation

The ellipsometry data will be correlated with the infrared data

Off-line investigation of the stretching process by FTIR


28

AcknowledgementAcknowledgement

Otto van Asselen, TU/eOtto van Asselen, TU/e

Edgar Karssenberg, TU/eEdgar Karssenberg, TU/e

Martin van Duin, DSM Research, Geleen, The Martin van Duin, DSM Research, Geleen, The

NetherlandsNetherlands

Gert de Wit, GE Advanced Materials, Bergen op Gert de Wit, GE Advanced Materials, Bergen op

Zoom, The NetherlandsZoom, The Netherlands

Colleagues in the faculty of Chemical Colleagues in the faculty of Chemical

Engineering & Chemistry of TU/eEngineering & Chemistry of TU/e


29

Thanks for your Thanks for your attention !attention !


30


31

Morphology developement viscosity of phases,interfacial properties, blend composition,

processing conditions

IntroductionIntroduction



32

Capillary Number ---- Drop deformation

R

R

C c

.

a

size. Drop R

tensionlInterfacia

stressShear


33

Why oxazoline??Why oxazoline??

Macosko et al., Polymer 42 (2001), 8171

P

O

OH P' NH2+

P

O

OH P' O

O

O+P OH

O

O

OP'

+

P NH2 P' O

O

O

+P' NH2

O

O

OP

+

O

NP'P

O

OH +

P(arom.) < P(aliph.) P’(arom.) < P’(aliph.)


34

EllipsometryEllipsometry The evolution of interface with time under

different temperatures


35

Model for Ellipsometry


36

Off-line investigation of the stretching process by FTIR


37

FTIR Microscopy


38

Conversion of oxazolineConversion of oxazolineconersion of oxa at 983cm-1 under 190deg

0.0000

10.0000

20.0000

30.0000

40.0000

50.0000

60.0000

70.0000

80.0000

90.0000

100.0000

0.0000 50.0000 100.0000 150.0000 200.0000

time/min

convers

ion/ %

boarderbaseline in diffspeccurve f itting

narrow erbaseline in diffspec

Conversion of oxa under 170deg

-10.0000

0.0000

10.0000

20.0000

30.0000

40.0000

50.0000

60.0000

70.0000

0 20 40 60 80 100 120 140 160

time/min

conv

ersi

on/ %

1660 boarder baseline

983 boarder baseline

1660->980

curve f itting for 983cm-1

Which one is better


39

5.4% SAN-oxa with catalyst 5.4% SAN-oxa with catalyst

5.4% without catalyst 190deg 2hrs


40

5.4% with 55wt% catalyst (to oxazoline) 190deg 2hrs

faculty of chemical engineering & chemistry 1 monitoring interlayer formation by infrared...

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