侧基差异对含磷、 氟、 氧和硅烷聚合物构象性质的影响

doi:10.7503/cjcu20180155

摘要/Abstract

摘要：

基于改进的旋转异构态模型和生成矩阵统计方法, 推导了均方回转半径和均方偶极矩的公式, 并应用于研究无机和半无机聚合物构象-构型依赖的性质. 计算结果发现, 聚合物链的柔性和极性与含杂元素成分、侧基的大小、构象能及链规整程度有关, 不对称链比对称链极性更强. 聚甲基苯基硅烷(PMPS)和聚二甲基亚硅烷(PDMS)与聚甲基苯基硅醚、聚苯基硅烷和聚磷酸等相比, 因侧基高密集分布导致链尺寸较大. 尤其是PMPS, 其长链在考虑侧基与不考虑侧基影响下计算的链尺寸差异为4.68%, 特性黏数随构型参数和链聚合度增大有较大的变化. 同样, PDMS的温度系数随链聚合度增大有独特的变化规律. 因此, 建议在计算分子链尺寸和极性时, 不能忽略侧基的大小、分布和极性.

关键词: 聚甲基苯基硅烷, 聚磷酸, 特性率, 特性黏数, 温度系数, 构象, 构型, 均方回转半径, 均方偶极矩

Abstract:

Formulas of mean-square radius of gyration and mean-square dipole moment were deduced by the improved rotational-isomeric-state model and the generator matrix method. The configuration-conformation dependent properties of inorganic and semi-inorganic polymers were investigated by these basic quantities. From comparing the calculated results, it is found that the flexibility and polarity of chain are related to the heteroatom constituents, the size of side group, the conformation energies and tacticity of chain. The polarity of asymmetric polymers is greater than that of symmetric polymers. Duo to existence the crowd side groups, poly(methylphenylsilylene)(PMPS) and poly(dimethylsilylene)(PDMS) have greater chain dimensions than those of poly(methlphenysiloxanc), poly(silastyrene) and polyphosphate. Especially, the dimensions of PMPS chain with and without considering side group have a difference of 4.68%. The intrinsic viscosity changes obviously as configuration parameters and degree of polymerization increase. Similarly, the temperature coefficients of PDMS also change uniquely as degree of polymerization increase. Therefore, it suggests that the size, distribution and polar of side groups cannot be neglected in estimating the dimension and polarity of polymers.

Key words: Poly(methylphenylsilylene), Polyphosphate, Characteristic ratio, Intrinsic viscosity, Temperature coefficient, Configuration, Confromation, Mean-square radius gyration, Mean-square dipole moment

中图分类号:

O631.2

TrendMD:

马海珠, 韩文韬, 陶飞. 侧基差异对含磷、氟、氧和硅烷聚合物构象性质的影响. 高等学校化学学报, 2018, 39(10): 2304.

MA Haizhu,HAN Wentao,TAO Fei. Effect of Side Groups on Conformational Characteristics of Containing Phosphor, Fluoride, Oxygen and Silane Polymers^†. Chem. J. Chinese Universities, 2018, 39(10): 2304.

图/表 10

Fig.1 Relation of PMPS structure and -[A(b)-D(e)]x- model(A), relationship between successive bonds for the anti(B) and syn(C) configurations of phenyl group

Table 1 Mass of sequence m(q) and the matric elements of D(q) and A(q)

q	m(q)	D(q)=gen[d₁₂,d₁₃,d₂₂,d₂₃]				A(q)=gen[a₁₂,a₁₃,a₂₂,a₂₃]
q	m(q)	d₁₂	d₁₃	d₂₂	d₂₃	a₁₂	a₁₃	a₂₂	a₂₃
1	1	m_AJ_Pg_D	m_Am_D $l D 2$	g_D	m_Dg_DJ_Q	m_DJ_Pg_A	m_Am_D $l A 2$	g_A	m_Ag_AJ_Q
2	m_Dm_b	0	0	g_D	0	J_Pg_A	$r Db 2$	g_A	g_ag_bJ_Q
3	m_bm_D	J_Pg_cg_d	$r bD 2$	g_D	g_DJ_Q	0	0	g_A	0
4	m_Am_b	0	0	g_D	0	J_P	$l b 2$	g_A	g_ag_bJ_Q
5	m_bm_A	J_Pg_cg_d	0	g_D	J_Q	0	0	g_A	0
6	m_bm_b	J_Pg_cg_d	0	g_D	0	0	0	g_A	g_ag_bJ_Q
7	m_Dm_e	J_P	$l e 2$	g_D	g_dg_eJ_Q	0	0	g_A	0
8	m_em_D	0	0	g_D	0	J_Pg_fg_a	0	g_A	J_Q
9	m_Am_e	J_Pg_D	$r Ae 2$	g_D	g_dg_eJ_Q	0	0	g_A	0
10	m_em_A	0	0	g_D	0	J_Pg_fg_a	$r eA 2$	g_A	g_AJ_Q
11	m_bm_e	J_Pg_cg_d	0	g_D	g_dg_eJ_Q	0	0	g_A	0
12	m_em_b	0	0	g_D	0	J_Pg_fg_a	0	g_A	g_ag_bJ_Q
13	m_em_e	0	0	g_D	g_dg_eJ_Q	J_Pg_fg_a	0	g_A	0

Table 1 Mass of sequence m(q) and the matric elements of D(q) and A(q)

q	m(q)	D(q)=gen[d₁₂,d₁₃,d₂₂,d₂₃]				A(q)=gen[a₁₂,a₁₃,a₂₂,a₂₃]
q	m(q)	d₁₂	d₁₃	d₂₂	d₂₃	a₁₂	a₁₃	a₂₂	a₂₃
1	1	m_AJ_Pg_D	m_Am_D $l D 2$	g_D	m_Dg_DJ_Q	m_DJ_Pg_A	m_Am_D $l A 2$	g_A	m_Ag_AJ_Q
2	m_Dm_b	0	0	g_D	0	J_Pg_A	$r Db 2$	g_A	g_ag_bJ_Q
3	m_bm_D	J_Pg_cg_d	$r bD 2$	g_D	g_DJ_Q	0	0	g_A	0
4	m_Am_b	0	0	g_D	0	J_P	$l b 2$	g_A	g_ag_bJ_Q
5	m_bm_A	J_Pg_cg_d	0	g_D	J_Q	0	0	g_A	0
6	m_bm_b	J_Pg_cg_d	0	g_D	0	0	0	g_A	g_ag_bJ_Q
7	m_Dm_e	J_P	$l e 2$	g_D	g_dg_eJ_Q	0	0	g_A	0
8	m_em_D	0	0	g_D	0	J_Pg_fg_a	0	g_A	J_Q
9	m_Am_e	J_Pg_D	$r Ae 2$	g_D	g_dg_eJ_Q	0	0	g_A	0
10	m_em_A	0	0	g_D	0	J_Pg_fg_a	$r eA 2$	g_A	g_AJ_Q
11	m_bm_e	J_Pg_cg_d	0	g_D	g_dg_eJ_Q	0	0	g_A	0
12	m_em_b	0	0	g_D	0	J_Pg_fg_a	0	g_A	g_ag_bJ_Q
13	m_em_e	0	0	g_D	g_dg_eJ_Q	J_Pg_fg_a	0	g_A	0

Table 2 Statistical weight matrix of polymers

Series	t, g^±	u_A	u_F or u_D
PS, PDMS^[9,10]	0°, ±125°	$1 σ σ 1 σψ σω 1 σω σψ$	$1 σ σ 1 σψ σω 1 σω σψ$
PP^[21,22]	0°, ±120°	$111100100$	$111100100$
PDVF^[24]	0°, ±120°	$0.607 0.848 0.848 0.848 1 0.770 0.848 0.770 1$	$1 0.559 0.559 0.559 0.224 0.124 0.559 0.124 0.224$
PDMSM^[14]	0°, ±115°	$111111111$	$111110101$
PMPS^[6]	11°, 120°	u_Dm=u_Am= $0.144 0.044 0.044 0.076$	u_Dr=u_Ar= $1.0 0.017 0.017 0$

Table 2 Statistical weight matrix of polymers

Series	t, g^±	u_A	u_F or u_D
PS, PDMS^[9,10]	0°, ±125°	$1 σ σ 1 σψ σω 1 σω σψ$	$1 σ σ 1 σψ σω 1 σω σψ$
PP^[21,22]	0°, ±120°	$111100100$	$111100100$
PDVF^[24]	0°, ±120°	$0.607 0.848 0.848 0.848 1 0.770 0.848 0.770 1$	$1 0.559 0.559 0.559 0.224 0.124 0.559 0.124 0.224$
PDMSM^[14]	0°, ±115°	$111111111$	$111110101$
PMPS^[6]	11°, 120°	u_Dm=u_Am= $0.144 0.044 0.044 0.076$	u_Dr=u_Ar= $1.0 0.017 0.017 0$

Fig.2 Dependence of the characteristic ratio on degree of polymerization(A) Sn=<S2>/2xl2; (B) Dn=<μ2>/xμ02. a. PDMS; b. a-PSS; c. PP; d. a-PMPSO; e. a-PMPSO without considering side group; f. PDVF; g. PS; h. PDMSM; i. a-PSP.

Fig.3 Dependence of the characteristic ratio of PMPS chain on degree of polymerization(A) Sn=<S2>/2xl2 ; (B) Dn=<μ2>/xμ02. a. wm=0; b. wm=0.1; c. wm=0.2; d. wm=0.5;e. wm=1.0(without considering side group); f. wm=0.5; g. wm=1.0.

Fig.4 Dependence of the characteristic ratios on the angles of internal rotation(A) φg=120°; (B) φt=11° . a, c. Sn(a-PMPS); b, d. Dn(i-PMPS).

Fig.5 Dependence of the intrinsic viscosity(A) and the characteristic ratio(B) on the fraction of meso dyad

Fig.6 Dependence of the temperature coefficients on degree of polymerization(A) κS; (B) κD. a. a-PSP; b. a-PMPSO; c. a-PSS; d. PS; e. PDMS.

Fig.7 Dependence of the temperature coefficients on the fraction of meso dyad

Fig.8 Dependence of the intrinsic viscosity on the degree of polymerization

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