Professor: Cheng-Ho Chen
Graduate: Po-Huei Tseng
Date: 101.12.19
Outline
 Introduction
 Experiment
 Results and Discussion
 Conclusions
 References
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Introduction(1)
 Ionomers: macromolecules composed of a small but
significant proportion of constitutional units (less than
10%) containing an ionic and/or ionizable group.
 The ionic groups cause a micro-phase separation of the
ionic moieties (ionic aggregation) within the non-ionic
matrix and act as physical crosslinks.
 Ionomers of low glass-transition non-crystalline polymers
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can be used as ionic thermoplastic elastomers (TPEs) if
the ionic aggregates are sufficiently weakened at the
processing temperatures.
Introduction(2)
 TPEs: melt-processable polymers composed of a
continuous elastomeric phase.
 Both the precursor elPP-g-MA and the ionomers were
synthesized by melt-processing.
 The neutralization reaction was monitored by infrared
spectroscopy and a method is proposed to determine the
effective neutralization degree (ND).
 Various forms of sodium hydroxide and sodium acetate
were used to compare their efficiency of elPP-g-MA
neutralization.
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Outline
 Introduction
 Experiment
 Results and Discussion
 Conclusions
 References
5
Materials
Materials
Isotactic homopolymer PP powder
2,5-bis(tert-butyl-peroxy)2,5dimethylhexane[DHBP]
Purchase
Purity
Moplen HF500N
Basell
50 wt% blend
with Si
Arkema
Maleic anhydride(MA)
99%
Acros
N-bromosuccinimide(NBS)
99%
Acros
Sodium Acetate Trihydrate
(NaAcTH)
99%
Aldrich
NaOH(pellets)
99+%
Aldrich
NaOH(powder)
97%
Aldrich
Sodium Acetate Anhydrous(SAA)
99%
Aldrich
Tolune(analytical grade)
Luperox
101XLS50
Company
Fisher
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Equipments
Equipments
DSC
SEC
FTIR
TGA
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Model
DSC 821e
GPCV 2000
Nexus 670
TGA/SDTA 851e
Manufacturer
Mettler Toledo
Waters Alliance
Nicolet
Mettler Toledo
Synthesis 1 elPP-g-MA
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Synthesis 2 Ionomer
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Characterization
 Quantification of the grafted species
 Differential scanning calorimetry (DSC)
 Size exclusion chromatography(SEC)
 Fourier transform infrared (FTIR)
spectroscopy
 Thermogravimetric analysis (TGA)
 Rheological properties
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Quantification of the grafted species
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DSC
 Crystallinity and Tg of elPP-g-MA and ionomers:
evaluated from a second heating ramp from -50 to
220℃ at 10℃/min.
 The device was calibrated with indium and zinc.
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SEC
 The mobile phase: 1,2,4-trichlorobenzene(TCB)
 The concentration of the sample:
2 mg/mL in TCB
 dissolution: shaking at 160℃ for 1 h
 The injection volume: 215 μL
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 Temperature: held constant at 145℃
FTIR
 the peak height of the 973 cm-1 absorption
band to an absorbance of 1
 The frequency range of absorption bands area:
1.carbonyl of the anhydride (1750-1830 cm-1)
2.carbonyl of the carboxylic acid (1650-1750
cm-1)
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TGA
 heating rate: 10℃/min under air
atmosphere(100 mL/min)
 temperature: 25-600℃
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Rheological properties
 Equipment:
Rubber Process Analyser RPA 2000, Alpha
Technologies
 Frequency sweep tests:
 performed at 120℃
 at a strain rate of 10% over an angular
frequency ranging from 300 to 1 rad/s
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Outline
 Introduction
 Experiment
 Results and Discussion
 Conclusions
 References
17
elPP-g-MA Characterization
The degradation of the molar mass is caused by a side reaction, β-scission,
occurring during the functionalization. The crystallinity of elPP-g-MA is strongly
reduced with respect to the starting PP, due to the epimerization reaction
occurring in the presence of peroxide and NBS.
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Ionomer ND determination(1)
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Ionomer ND determination(2)
1790
1715
1863
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1570
Ionomer ND determination(3)
 If the ND were calculated on the basis of the decrease of
the anhydride band at 1790 cm-1 from elPP-g-MA
(AanhelPP-g-MA) to ionomer (Aanhionomer), it would be
overestimated due to the carboxylic acid functions
contribution.
ND 
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Aanhionomer
AanhelPPg MA
100
Ionomer ND determination(4)
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Influence of the nature of the base on ND
NaOH 2.5 M > NaOH sol. ≒ NaAc*3H2O sol. > NaAc 2.5 M > NaAc. anh. sol.
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Ionomer Characterization
 DSC
 TGA
 Rheology
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DSC
 elPP-g-MA: Tg is around -4.2℃ and a weak
broad melting peak.
 Ionomers: only Tg
 Tg for all the ionomers are similar to the one of
elPP-g-MA.
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TGA
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Rheology
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Conclusions
 The choice of the base has a strong influence on the
neutralization degree.
 As the neutralization yield never reaches 100%, the excess
of the added sodium hydroxide may lead to corrosion.
 Sodium acetate is preferred over sodium hydroxide.
 The thermal stability in air atmosphere, shear storage
modulus and complex viscosity in the flow region were
largely increased as a function of the neutralization degree.
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