Intramolecular Reaction in Self-condensing Vinyl Polymerization System with Solvent Effect†

doi:10.7503/cjcu20160824

Abstract

Abstract:

We present the effect of intramolecular reaction on the average properties of hyperbranched polymers formed in the self-condensing vinyl polymerization system by the method of Monte Carlo simulation. A model to specify the generations of all units in a branched polymer was proposed to model intramolecular reaction, from which a set of kinetic differential equations was given to describe the growth of various polymers. The simulation was performed by means of the intermolecular and intramolecular reaction rates under different solvent conditions. As a result, the number of treelike and cyclic polymers, the size distribution of rings and weight-average molecular weights were obtained, by which the effect of cyclization on the average properties of polymers was discussed. Furthermore, it is shown that cyclization depends on the cooperation of monomer concentration and solvent quality, where monomer concentration plays a key role in intramolecular reaction, while solvent quality becomes significant only at a high concentration. It is expected that the present study is helpful to design the related materials.

Key words: Self-condensing vinyl polymerization, Hyperbranched polymer, Generation model, Intramolecular reaction, Solvent effect

CLC Number:

O631
O641

TrendMD:

WANG Yunming, CHANG Peiyang, GU Fang, WANG Haijun. Intramolecular Reaction in Self-condensing Vinyl Polymerization System with Solvent Effect^†[J]. Chem. J. Chinese Universities, 2017, 38(4): 660.

Figures/Tables 12

Fig.1 Schematic illustration of the formation of a 5-membered ring in treelike polymer of 11-mer

Table 1 Scaling exponents α under various concentrations and solvent qualities

Solvent quality and concentration	α	Solvent quality and concentration	α
Good solvent and dilute solution	$5 2 (d + 2)$	Concentrated solution or melt	$1 d$
Θ-solvent and dilute solution	$7 4 (d + 1)$	Zimm-stockmayer: mean field theory	$14$

Table 1 Scaling exponents α under various concentrations and solvent qualities

Solvent quality and concentration	α	Solvent quality and concentration	α
Good solvent and dilute solution	$5 2 (d + 2)$	Concentrated solution or melt	$1 d$
Θ-solvent and dilute solution	$7 4 (d + 1)$	Zimm-stockmayer: mean field theory	$14$

Table 2 Reaction types and probabilities in the present SCVP system

Reaction type	Probability	Reaction type	Probability
P_i+P_n-i→P_n	knP_iP_n-i/2 $Ω T n$	P_n-i+R_i→R_n	k $∑ m$ iP_n-i $R i (m)$ / $Ω R n$
P_n→R_n	$∑ i, m k R, n (m) B n (m)$ (i)/ $Ω R n$	P_n-i+ $R i (m)$ → $R n (m)$	iP_n-i $R i (m)$ /[ $∑ m$ iP_n-i $R i (m)$ ]
P_n→ $R n (m)$	$∑ i k R, n (m) B n (m)$ (i)/[ $∑ i, m k R, n (m) B n (m)$ (i)]

Table 2 Reaction types and probabilities in the present SCVP system

Reaction type	Probability	Reaction type	Probability
P_i+P_n-i→P_n	knP_iP_n-i/2 $Ω T n$	P_n-i+R_i→R_n	k $∑ m$ iP_n-i $R i (m)$ / $Ω R n$
P_n→R_n	$∑ i, m k R, n (m) B n (m)$ (i)/ $Ω R n$	P_n-i+ $R i (m)$ → $R n (m)$	iP_n-i $R i (m)$ /[ $∑ m$ iP_n-i $R i (m)$ ]
P_n→ $R n (m)$	$∑ i k R, n (m) B n (m)$ (i)/[ $∑ i, m k R, n (m) B n (m)$ (i)]

Fig.2 Plots of Mn(a) and Mw(b) against conversion p in SCVP system without cyclizationThe inset is the plot of Pn with p=0.98 against n.

Fig.3 Plots of R(m) against p and m in SCVP system in a dilute good solvent(A, ϕ=0.01, α=1/2) and in a concentration solution(B, ϕ=0.5, α=1/3)

Fig.4 Plots of Mw and PI(inset) against p in SCVP system for the cases of ϕ=0.01 and α=1/2, ϕ=0.5 and α=1/3 and without cyclization

Fig.5 Plots of MTw(a, a') and MRw(b, b') against p in SCVP system under the same conditions as in Fig.3a, b. ϕ=0.01, α=1/2; a', b'. ϕ=0.5, α=1/3.

Fig.6 Plots of pT(a, b) and pR(a', b') against p in SCVP system under the same conditions as in Fig.3a, a'. ϕ=0.01, α=1/2; b', b'. ϕ=0.5, α=1/3.

Fig.7 Plots of fR(a, b) and fRunit(a', b') against p in SCVP system under the same conditions as in Fig.3a, a'. ϕ=0.01, α=1/2; b', b'. ϕ=0.5, α=1/3.

Fig.8 Plots of pR and fRunit(inset) against p in SCVP system for α=7/16, α=1/3 and different ϕ

Fig.9 Plots of pR/p and pR against p in SCVP system for different ϕ and α

Fig.10 Plots of fRunit against p in SCVP system for different ϕ and α

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