Professor: Cheng-Ho Chen Graduate: Po-Huei Tseng Date: 101.12.19.

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Professor: Cheng-Ho ChenGraduate: Po-Huei Tseng

Date: 101.12.19

OutlineIntroductionExperimentResults and DiscussionConclusionsReferences

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 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.

MaterialsMaterials Purchase Purity Company

Isotactic homopolymer PP powder Moplen HF500N Basell

2,5-bis(tert-butyl-peroxy)-2,5dimethylhexane[DHBP]

Luperox 101XLS50

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) Fisher6

Equipments

Equipments Model Manufacturer

DSC DSC 821e Mettler Toledo

SEC GPCV 2000 Waters Alliance

FTIR Nexus 670 Nicolet

TGA TGA/SDTA 851e Mettler Toledo

Synthesis 1 elPP-g-MA

Synthesis 2 Ionomer

Characterization

Quantification of the grafted speciesDifferential scanning calorimetry (DSC)Size exclusion chromatography(SEC)Fourier transform infrared (FTIR)

spectroscopyThermogravimetric analysis (TGA)Rheological properties

Quantification of the grafted species

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.

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 μLTemperature: held constant at 145℃

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

heating rate: 10℃/min under air atmosphere(100 mL/min)

temperature: 25-600℃

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

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.

Ionomer ND determination(1)

15701715

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.

100ND MAgelPP

ionomer

Influence of the nature of the base on ND

NaOH 2.5 M > NaOH sol. NaAc*3H≒ 2O sol. > NaAc 2.5 M > NaAc. anh. sol.

Ionomer CharacterizationDSCTGARheology

DSCelPP-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.

Rheology

ConclusionsThe 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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Professor: Cheng-Ho Chen Graduate: Po-Huei Tseng Date: 101.12.19.

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