A comprehensive analysis for styrene and its derivatives ...

National Yunlin University of Science and Technology Department of Safety, Health, and Environmental Engineering

Process Safety & Disaster Prevention Laboratory

A comprehensive analysis for styrene and its derivatives by calorimeters and spectrometers

Reporter: Kwan-Hua Hu

October 24, 2006 (Tuesday)

Process Safety & Disaster Prevention Laboratory (PS&DPL), Department of Safety, Health, and Environmental Engineering, National Yunlin University of Science and Technology

Mary Kay O’Connor Process Safety CenterThe Brazos Center, College Station, Texas

Sheng-Yi Lin, Jo-Ming Tseng , Chi-Min Shu*, Yan-Fu Lin, Chia-Chun Liao



Syllabus

Introduction

Literature reviews

Experiments

Results and discussion

Conclusions

Recommendations

Publications

Future Prospects

Acknowledgements



Unsaturated polyesters, UP

Styrene-butadiene elastomers

Acrylonitrile-butadiene-styrene terpolymers, ABS

Emulsion polymers, EP

Homopolystyrene

Styrene-acrylonitrile copolymers,SAN

Miscellaneous

Introduction (1/5)

Styrene:1. Characteristics. 2. Process. 3. Purpose.

Global outturn:1. Asia. 2. Europe. 3. USA.

Fig. 1. Various high economic products derived from styrene.



The main causes of accident incurred by styrene, derivatives, and its isomers were external and internally unsafe acts in Asia, Europe, and USA, as follows:

1. Human. 2. Equipment.3. Environment. 4. Others.

Introduction (2/5)



Introduction (3/5)

α-Methylstyrene (AMS).

Trans-β-methylstyrene (TBMS).

The aim of this study was to:(1) estimate thermokinetics parameters and identify polymerization mechanisms; (2) apply practical polymerization process; and(3) alleviate individual thermal hazard of accident occurrence to an acceptable level.

Fig. 3. Trans-β-methylstyrene (TBMS).Fig. 2. α-Methylstyrene (AMS).

C

CH3

H2C

Comparison

CHHC

CH3



Fig. 4. The flowchart of manufacturing process on AMS.

Introduction (4/5)

CHH3C CH3

CH3CH＝CH2+95℃AlCl3

CHH3C CH3

ΔCatalyst

+ H2

C CH2H3C

Tar TarBenzene

Isopropyl Benzene

Production

Isopropyl Benzene

Dehydrogenation

Steam

Hydrochloric Acid Gas

Aluminum Chloride

Propylene Chloride

Benzene Chloride

Isopropyl Benzene

Styrene

Toluene

α-methylstyrene

ρ-TertiaryButyl Catechol

(Inhibitor)

α-methylstyreneFinishing



Introduction (5/5)

Fig. 5. The flowchart of experimental procedure.

Differential scanning calorimetry (DSC)

Thermal activity monitor (TAM)

Styrene

Selected accidents occurred in Asia, Europe, and USA

Styrene containing 4-tert-butylcatechol (TBC) α-Methylstyrene (AMS)

Trans-β-methylstyrene(TBMS)

Ortho-methylstyrene (OMS)Meta-methylstyrene (MMS)Para-methylstyrene (PMS)

Blast furnace

Thermokinetic parameters estimation and polymerization mechanisms identification

Fourier transform infrared absorption spectrophotometer (FT-IR)

Nuclear magnetic resonance spectrometer (NMR)



Fig. 6. Historical background on styrene development.

1936Be specific

1937Paul J. Flory

1953Frank R. Mayo

1960Frank R. Mayo

1968Frank R. Mayo

1970William A. Pryor

2002 Chin-Chuan Chen

2003Jy-Jinn Wei

1839Simonin

1845Blyth and Hoffman

2001Kothe and Fischer

1920–1930Be specific

After 18th centurySimon

About 18th centuryNeuman

1831Bonastre

1952Zimm and Bragg

Literature Reviews (1/2)



Fig. 7. Historical background on α-methylstyrene, trans-β-methylstyrene, and its isomers development.

α-Methylstyrene Trans-β-methylstyrene

Para-methylstyrene

Meta-methylstyrene

Ortho-methylstyrene

1989Chaudhuri and Sharma1

1971Magagnini et al.

－

1966Prishchepa et al.

1994Taskinen et al.

1993Abu-Abdoun and Aale-Ali

1996Sun et al.

1996Ciminale et al.

1997Heidekum et al.

1999Chaudhuri

2005Cai et al.

2000Fujiwara et al.

Literature Reviews (2/2)



1. Differential scanning calorimetry (DSC)

• Method –The dynamic screening experiment performed on a Mettler TA 8000 system coupled with a DSC821e cell.

• Conditions – For the sake of better thermal equilibrium, the scanning rate for the temperature-programmed ramp was chosen to be 4 ℃/min.

• Obtained data – Exothermic onset temperature, isothermal heat flow, enthalpy, etc.

Fig. 8. Differential scanning calorimetry.

2. Thermal activity monitor (TAM)

• Method – Sample were dispensed into the disposable calorimetric glass and stainless contains, capped and then respectively placed in the measuring and reference chambers.

• Conditions–Measurements were conducted isothermally in the temperature range from 12 to 90℃.

• Obtained data– Heat power, enthalpy, isothermal time to maximum rate, etc.

Fig. 9. Thermal activity monitor.

Experiments (1/2)



Experiments (2/2)

4. Nuclear magnetic resonance spectrometer (NMR)

Fig. 11. Nuclear magnetic resonance spectrometer.

3. Fourier transform infrared absorption spectrophotometer (FT-IR)

Fig. 10. Fourier transform infrared absorption spectrophotometer.

In infrared spectroscopy, FT-IR radiation passes through a sample, which results in vibration transitions in functional groups.

The resulting spectrum represents the molecular absorption and transmission, creating a molecular fingerprint of the sample for spectroscopic identification.

The solution NMR spectrum was obtained on a varian GEMINI 300 spectrometer, the solution spectra were obtained in quantitative conditions.

All solid state spectra were obtained on a varian INOVA 300 spectrometer.



Fig. 12. Comparisons of dimerization and thermal polymerization curves of styrene, styrene containing 10 ppm TBC, AMS, and TBMS by DSC tests.

Results and discussion (1/17)

25 50 75 100 125 150 175 200 225 250 275 300 325 350 375 400 425 450 475 500-0.5

-0.4

-0.3

-0.2

-0.1

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

Trans-beta-methylstyrene9411137.4000 mgintegral 277.30 J/g

Alpha-methylstyrene9304267.9000 mgintegral 266.28 J/g

Styrene (with 10 ppm TBC)9110053.4000 mgintegral 597.56 J/g

Styrene (without TBC)9105099.5000 mgintegral 601.73 J/g

Hea

t Pow

er (m

W)

Temperature (℃ )



O

OH

CH3C

CH3

CH3

HR O

OH

CH3C

CH3

CH3

OH

CH3C

CH3

CH3

O

OH

CH3C

CH3

CH3

O

O

CH3C

CH3

CH3

O

H R O

CH3C

CH3

CH3

O

O

CH3C

CH3

CH3

O

Fig. 13. The flowchart for inhibition behavior by TBC.




Fig. 14. Comparisons of dimerization and thermal polymerization curves of OMS, MMS, and PMS by DSC tests.


25 50 75 100 125 150 175 200 225 250 275 300 325 3500.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

Ortho-methylstyrene9502073.9000 mgIntegral 400.33 J/g

Meta-methylstyrene9502083.0000 mgIntegral 463.92 J/g

Para-methylstyrene9502094.2000 mgIntegral 327.65 J/g

Hea

t Pow

er (m

W)

Temperature (℃ )



∆ ∆∆

Fig. 15. The energy level of resonance form on OMS, MMS, and PMS.




285.11147.83285.11140.06p-Methylstyrene

447.42190.48447.42184.35m-Methylstyrene

369.95206.82369.95201.64o-Methylstyrene

Exothermic peak temperature(Tmax, ℃)

Reaction heat(ΔH, J/g)

Exothermic onset temperature(T0, ℃)

Total exothermic

amount(Qtotal, J/g)

Dimerization

291.93439.91249.33388.50109.0042.6089.65Trans-β-methylstyrene

284.28405.75264.80360.20142.1819.48138.20α-Methylstyrene



Exothermic onset

temperature(T0, ℃)



Exothermic onset

temperature(T0, ℃)

Total exothermic

amount(Qtotal, J/g)

Thermal polymerizationDimerization

601.74204.53601.74134.05Styrene containing 10 ppm TBC

600.44205.82600.44104.60Styrene



Exothermic onset temperature(T0, ℃)

Total exothermic

amount(Qtotal, J/g)

Thermal polymerization

Fig. 16. The dynamic scanning data for styrene, styrene containing 10 ppm TBC, AMS, and TBMS.




Fig. 17. Comparison of polymerization curves of 2-chlorostyrene, 2,3,4,5,6-pentaflorostyrene, styrene, and styrene-D8.


+ F2+ Cl2




0 1 2 3 4 5 6 7-1

0

1

2

3

4

5

6

7

alpha-methylstyrene941106 (70℃ )0.5428 gIntegral 9.8985 J/g

alpha-methylstyrene940901 (70℃ )0.4572 gIntegral 12.8600 J/galpha-methylstyrene

940810 (75℃ )0.5305 gIntegral 13.2513 J/g

alpha-methylstyrene940814 (75℃ )0.5024 gIntegral 13.9230 J/galpha-methylstyrene

940729 (80℃ )0.4975 gIntegral 14.5192 J/g






Hea

t Pow

er (m

W/g

)

Time (day)

Fig. 18. Heat power vs. time for polymerization of 99 wt% AMS under various isothermal conditions by TAM tests.




Fig. 19. Heat power vs. time for polymerization of 99 wt% TBMS under various isothermal conditions.

0.0 0.4 0.8 1.2 1.6-18

-15

-12

-9

-6

-3

0

3

trans-beta-methylstyrene941002 (50℃ )0.4962 gIntegral 11.9385 J/g

Hea

t Pow

er (m

W/g

)

Time (day)

0.0 0.2 0.4 0.6 0.8

-16

-12

-8

-4

0

4

8

trans-beta-methylstyrene940728 (90℃ )0.2910 g

trans-beta-methylstyrene940727 (90℃ )0.2691 g

Hea

t Pow

er (m

W/g

)

Time (day)




Fig. 20. The blast furnace tests on AMS and TBMS (1).

90℃ 50℃70℃ 90℃

180℃ (B.) 180℃ (A.) 180℃ (B.)

Diels-Alder reaction Retro-Diels-Alder reaction

AMS TBMS

180℃ (A.)



Diels-Alder reaction and Retro-Diels-Alder reaction, dimerization.

Free radical reaction, unsaturated and saturated dimer, thermal polymerization.

Initial reaction of styrene.

Fig. 21. Infrared absorption spectra of polymerization of AMS conducted by FT–IR.

Fig. 22. Infrared absorption spectra of polymerization of TBMS conducted by FT–IR.





C CH2

CH3

HC CH

CH3

Fig. 23. Nuclear magnetic resonance spectra of polymerization of AMS tested by NMR.

Fig. 24. Nuclear magnetic resonance spectra of polymerization of TBMS tested by NMR.

Ar－HBenzene ring(6.00) 6.60–8.00 (9.50)

CH2＝C－Conjectured5.30–5.70 (6.25)

Ar－CH3(2.10) 2.25–2.50

α-Methylstyrene spectrumStructure

Ar－HBenzene ring(6.00) 6.60–8.00 (9.50)

Ar－HNon-benzene ring(4.00) 6.20–8.60 (9.00)

Ar－CH3(2.10) 2.25–2.50

Trans-β-methylstyrene spectrumStructure

CCH2H3C

HCCH

CH3



CH2

CCCH2H3C

CH3

CH2

CCCH2H3C

CH3

CCH

CH2

C

H2C

CH3C

CH3

CHCH2

CH2

CHH2C

H2CHC

CH

CH3

CHHC

CH3

Fig. 25. The flowchart for dimerization on AMS.

Fig. 26. The flowchart for dimerization on TBMS.

HCCH

CH3

CHHC

CH3





Fig. 27. The blast furnace tests on AMS and TBMS (2).

360℃1 hr

360℃1 hr

360℃24 hr

360℃6 hr

360℃3 hr

360℃2 hr

360℃24 hr

360℃6 hr

360℃3 hr

360℃2 hr

C

CH3

H2C

CHHC

CH3



Fig. 28. Estimation of the polymerization mechanisms on AMS.




Fig. 29. Estimation of the polymerization mechanisms on TBMS.





[ ] [ ] 5.2AkdtAdR −=−=

}][]{[32 2

3

023

−−−=− AAkt

y = 0.0619x－0.0177R2 = 0.7812

-0.04

-0.02

0.00

0.02

0.04

0.06

0.08

0.10

0.12

0.14

0.16

0.18

0 0.5 1 1.5 2 2.5

Time (day )

－2/

3[[A

]－1.

5 －[A

] 0－1.

5 ] v

s －

kt

0.1530747393[A]2.02.4022388061852.010

0.1199820409[A]2.02.7528358212122.000

0.0495207757[A]1.54.2720895533291.501

0.0527282330[A]1.54.1552238813201.500

0.0223416180[A]1.05.7523880604431.010

0.0205961370[A]1.05.8952238814541.000

0.0079282118[A]0.57.2846268665610.501

0.0125711625[A]0.56.6873134335150.500

0.0041477734[A]07.8819402996070.001

0[A]08.7000000006700.000

－kt=2/3{[A] － 2/3 －[A0] － 2/3 }

Concentrations alteration

(M)

Concentrations

(M)

Heat valuealteration

(Q)

Reaction period

(day)

k = slope

= 0.0619 (1/day)

= 7.16×10－7 (1/sec)

2. Reaction rate constant:1. Reaction order:




2. Frequency factor:

1. Apparent activation energy:

(2) Ea2 = 84 (kJ/mol)

7.16 × 10－7 = A × e－84,000/8.314(273+70)

A = 4.76×106 (1/sec)

(1) Ea1 = 67 (kJ/mol)

7.16 × 10－7 = A × e－67,000/8.314(273+70)

A = 1.22 × 104 (1/sec)0 2 4 6 8 10 12

-2.5

0.0

2.5

5.0

7.5

10.0

12.5

15.0

17.5

20.0

22.5

25.0

27.5

Styrene910401-1 (50℃ )0.2050 gintegral 550.0 J/g





Hea

t Pow

er (m

W/g

)

Time (day)

k = A × e－Ea/RT

Fig. 30. Heat power vs. time for polymerization of 99 mass% styrene under various isothermal conditions by TAM tests.

Ea1 = 67 (kJ/mol)

Ea2 = 84 (kJ/mol)



Conclusions

The thermal curves on AMS and TBMS both showed dimerization and thermal polymerization under dynamic scanning tests by DSC.

The initiation was triggered by Diels-Alder reaction from the dimerization of two AMS and two TBMS, respectively.

A mechanism of the thermal initiation process was also proposed and was similar to the mechanism for the thermal polymerization of styrene suggested by Mayo, 1960.

Through this study, isomers of different organic peroxides can be applied to have related polymerization mechanismsand thermal hazard estimations.



Recommendations

To identify the critical reaction step dominated with the dimerization by different substitutes, such as bromine, with functional group approaches.

From results gained by this investigation, the basis to acquire the related kinetic parameters could be adequately designed, established, implemented and evaluated to a deeper extent.



Future Prospects

Thermal Analysis

Chemical Engineering

Material Engineering

HCCH

CH3

CH3C CH2

HCCH2

CH

CH3

HCCH2

CH3

HCCH2

CH3



Acknowledgements

杜逸興 (仁德醫護管理專科學校職業安全衛生科)

洪肇嘉 (雲林科技大學環境與安全衛生工程系/所)

易逸波 (雲林科技大學環境與安全衛生工程系/所)

林彥甫 (中興大學化學系)

彭立祥 (正修科技大學化工與材料工程系)

王怡仁 (雲林科技大學化學工程系/所)

製程安全與防災實驗室所有成員



Thank you for your attention!

A comprehensive analysis for styrene and its derivatives ...

Documents

Transcript of A comprehensive analysis for styrene and its derivatives ...