Give the definition of the kinetics chain length >

Principles of Modern Chemistry
8th Edition
ISBN:9781305079113
Author:David W. Oxtoby, H. Pat Gillis, Laurie J. Butler
Publisher:David W. Oxtoby, H. Pat Gillis, Laurie J. Butler
Chapter23: Polymeric Materials And Soft Condensed Matter
Section: Chapter Questions
Problem 24AP
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2) Finally, the polymerization conditions were optimized to get a polymer which the
structure is shown below. The termination occurs 100% by coupling
(combination). Write the chemical structure of the initiator used and its
decomposition reaction. Give the definition of the initiator efficiency (f)
H₂C
CH3
CH₂
H₂C
CH-CH₂-
2-C-(CH₂=CH-C
H₂C
NC
CN
CH₂
3) What is the other possible mode of termination in conventional radical
polymerization?
4) Finally, poly(styrene) (PS) is prepared using [styrene] = 1 mol/L in toluene and
[initiator] = 5 x 10 mol/L.
Propagation rate: Rp = 6.62 x 10-6 mol/L/s
f=0.60
Demonstrate that the half-life of a radical initiator is t1/2 = 0.693/kd
5) Knowing that the ten hours half-life of the initiator (used for the synthesis of PS) is
achieved at 51 °C in toluene, calculate the constant ka
6) Calculate the initiation rate (R₂)
7) Give the definition of the kinetics chain length >
8)
Calculate the number average degree of polymerization (DP) assuming that the
termination occurs by combination only.
9) What is the value of Mn?
10) The DP, is determined experimentally by elemental analysis which gives the wt%
of nitrogen (N = 14) in the polymer. Which %N value is expected of which
experimental(s) method(s) could be used to confirm the value of DP?
11) After analyzing PS by size exclusion chromatography, the polydispersity (Đ) of the
polymer sample calculated is 2.1. Give the definition of polydispersity. Is this value
consistent with the polymerization method used ?
12) The polymer chemist was not satisfied by the value of Đ. He (she) decided to
change the polymerization method to obtain a PS sample with a polydispersity near
1. To this end, the following reaction is performed:
AIBN
60°C
What is the name of the polymerization method ? Write the chemical structure of
PS obtained in such conditions. What is the role of the dithioester (CPADB)?
-CH₂-CH
Transcribed Image Text:2) Finally, the polymerization conditions were optimized to get a polymer which the structure is shown below. The termination occurs 100% by coupling (combination). Write the chemical structure of the initiator used and its decomposition reaction. Give the definition of the initiator efficiency (f) H₂C CH3 CH₂ H₂C CH-CH₂- 2-C-(CH₂=CH-C H₂C NC CN CH₂ 3) What is the other possible mode of termination in conventional radical polymerization? 4) Finally, poly(styrene) (PS) is prepared using [styrene] = 1 mol/L in toluene and [initiator] = 5 x 10 mol/L. Propagation rate: Rp = 6.62 x 10-6 mol/L/s f=0.60 Demonstrate that the half-life of a radical initiator is t1/2 = 0.693/kd 5) Knowing that the ten hours half-life of the initiator (used for the synthesis of PS) is achieved at 51 °C in toluene, calculate the constant ka 6) Calculate the initiation rate (R₂) 7) Give the definition of the kinetics chain length > 8) Calculate the number average degree of polymerization (DP) assuming that the termination occurs by combination only. 9) What is the value of Mn? 10) The DP, is determined experimentally by elemental analysis which gives the wt% of nitrogen (N = 14) in the polymer. Which %N value is expected of which experimental(s) method(s) could be used to confirm the value of DP? 11) After analyzing PS by size exclusion chromatography, the polydispersity (Đ) of the polymer sample calculated is 2.1. Give the definition of polydispersity. Is this value consistent with the polymerization method used ? 12) The polymer chemist was not satisfied by the value of Đ. He (she) decided to change the polymerization method to obtain a PS sample with a polydispersity near 1. To this end, the following reaction is performed: AIBN 60°C What is the name of the polymerization method ? Write the chemical structure of PS obtained in such conditions. What is the role of the dithioester (CPADB)? -CH₂-CH
1) Styrene is polymerized by conventional radical polymerization using an azo
compound as a radical initiator that decomposes with heat. The polymer chemist
carried out the polymerization reaction without controlling the temperature. The
polymerization was performed at a very high temperature and he (she) isolated only
oligomers. How can you explain this?
Transcribed Image Text:1) Styrene is polymerized by conventional radical polymerization using an azo compound as a radical initiator that decomposes with heat. The polymer chemist carried out the polymerization reaction without controlling the temperature. The polymerization was performed at a very high temperature and he (she) isolated only oligomers. How can you explain this?
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