Nonlinear Elongational Rheology of Unentangled Poly（styrene-co-p-tert butyl styrene） Copolymers

doi:10.19894/j.issn.1000-0518.240050

Chinese Journal of Applied Chemistry ›› 2024, Vol. 41 ›› Issue (8): 1098-1106.DOI: 10.19894/j.issn.1000-0518.240050

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Nonlinear Elongational Rheology of Unentangled Poly（styrene-co-p-tert butyl styrene） Copolymers

Zong-Hao HONG¹^,², Shi-Long WU¹(), Quan CHEN¹^,²()

^1.State Key Laboratory of Polymer Physics and Chemistry，Changchun Institute of Applied Chemistry，Chinese Academy of Sciences，Changchun 130022，China
^2.School of Applied Chemistry and Engineering，University of Science and Technology of China，Hefei 230026，China

Received:2024-02-07 Accepted:2024-06-14 Published:2024-08-01 Online:2024-08-27
Contact: Shi-Long WU,Quan CHEN
About author:slwu@ciac.ac.cn
qchen@ciac.ac.cn
Supported by:
the National Natural Science Foundation of China(52103021)

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Abstract

Abstract:

Linear and nonlinear rheological properties were examined for unentangled polystyrene （PS）， poly（p-tert butyl styrene）（PtBS）， and their copolymer samples. All samples exhibited similar linear viscoelastic behavior， which was well predicted by the Rouse model owing to their similar average number of Kuhn segments per chain （about 30）. Under the fast uniaxial elongational flow （with Weissenberg number Wi＞1）， the sample exhibited “thickening” followed by “thinning” with increasing the elongational rate. This transition was attributable to the reduction of friction coefficient owing to the chains' coalignment along the elongational direction. Under the condition that the samples have a similar maximum stretch ratio λ_max= $n K$ （≈6）， the characteristic Wi for this transition increased with the content of tBS， reflecting that the tert-butyl groups may serve as the solvent to weaken the frictional reduction.

Key words: Polystyrene, Poly（p-tert butyl styrene）, Nonlinear elongational rheology

CLC Number:

O631

Zong-Hao HONG, Shi-Long WU, Quan CHEN. Nonlinear Elongational Rheology of Unentangled Poly（styrene-co-p-tert butyl styrene） Copolymers[J]. Chinese Journal of Applied Chemistry, 2024, 41(8): 1098-1106.

Figures/Tables 8

Fig.1 1H NMR spectrum of PS3-PtBS7

Table 1 Important parameters of the samples

Samples	f_PtBS/%	M_n/（kg·mol^-1）	M_w/（kg·mol^-1）	PDI	T_g/℃	n_K	τ_R /s
PS	0	19	24	1.26	102	26	0.001
PS7-PtBS3	35	23	29	1.26	115	27	0.008
PS5-PtBS5	54	29	35	1.22	123	30	0.09
PS3-PtBS7	74	38	49	1.29	132	37	0.63
PtBS	100	38	46	1.21	145	30	9.42

Fig.2 Light scattering responses of the products

Fig.3 DSC traces of PS， PtBS and their copolymer samples

Fig.4 LVE bTG'（diamond symbol） and bTG"（square symbol） master curves of the PS， PtBS， and their copolymer samples reduced at Tr=170 ℃ （wherein bTG' and bTG" are plotted against reduced frequency ωaT， the solid curves are fits to Eqs （1） and （2））

Fig.5 Comparison of normalized LVE master curves of the PS， PtBS， and their copolymer samples reduced at Tr=170 ℃， wherein G'Mw/ρRT and G"Mw/ρRT are plotted against reduced frequency ωτ， and G0=ρRT/Mw. The solid curves are fits to Eqs （3） and （4）

Fig.6 Plots of elongational stress growth coefficient （ηE+） against time （t） for PS， PtBS and their copolymers

Fig.7 （A） Plots of normalized steady-state viscosity ηE/ηE，0 against Wi for PS， PtBS， and their copolymers；（B） Plots of ηE/ηE，peak against normalized Weissenberg number Wi/Wipeak， wherein ηE，peak and Wipeak are the viscosity and Weissenberg number at the peak of ηE+，respectively

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Nonlinear Elongational Rheology of Unentangled Poly（styrene-co-p-tert butyl styrene） Copolymers

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