Effect of Side Groups on Conformational Characteristics of Containing Phosphor, Fluoride, Oxygen and Silane Polymers†

doi:10.7503/cjcu20180155

Abstract

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

CLC Number:

O631.2

TrendMD:

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

Figures/Tables 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

References 27

[1]	Harrah L.A., Zeigler J. M., Macromolecules, 1987, 20(3), 601—608
[2]	Ma H.Z., Cai H. H., Jin R. S., Scientia Sinica Chimica, 2012, 42(7), 1014—1021
	(马海珠, 蔡红红, 金璐师. 中国科学: 化学, 2012, 42(7), 1014—1021)
[3]	Zhou Z.P., Abe A., Macromolecules, 2003, 36(19), 7366—7371
[4]	Zhou Z.P., Abe A., Polymer, 2004, 45(4), 1313—1320
[5]	Ma H.Z., Wang Y. F., Ling F., Acta Polymerica Sinica, 2016, (5), 560—567
	(马海珠, 王一帆, 凌菲. 高分子学报, 2016, (5), 560—567)
[6]	Sundararajan P.R., Macromolecules, 1988, 21(5),1256—1261
[7]	Cotts P.M., Miller R. D., Trefonas P. T., West R., Fickes G. N., Macromolecules, 1987, 20(5), 1046—1052
[8]	Welsh W.J., Damewood J. R., West R. C., Macromolecules, 1989, 22(7), 2947—2951
[9]	Welsh W.J., DeBolt L., Mark J. E., Macromolecules, 1986, 19(12), 2978—2983
[10]	Damewood J.R. , West R., Macromolecules, 1985, 18(2),159—164
[11]	Sundararajan P.R., Macromolecules, 1991, 24(6), 1420—1422
[12]	Elias H.G., Vohwinkel F., New Commercial Polymer 2, Gordon and Breach Science Publishers,New York, 1986, 458—460
[13]	Cotts P.M., Miller R. D., Trefonas P. T., West R., Fickes G. N., Macromolecules, 1987, 20(5), 1046—1052
[14]	Mark J.E., Ko J. H., Macromolecules, 1975, 8(6), 874—878
[15]	Ko J.H., Mark J. E., Macromolecules, 1975, 8(6), 869—874
[16]	Wu X.Y., Jin J. S., Zhang L. X., Xu J. M., J. Polym. Sci.Part B, 1993, 31(4), 455—459
[17]	Bahar I., Zuniga I., Dodge R., Mattice W.L., Macromolecules, 1991, 24(10), 2993—2998
[18]	Sundararajan P.R., Macromolecules, 1990, 23(12), 3179—3183
[19]	Bacque E., Pillot J.P., Birot M., Dunogugs J., Macromolecules, 1988, 21(1), 34—38
[20]	Mark J.E., Ko J. H., J. Polym. Sci. Ploym. Phys. Ed., 1975, 13(11), 2221—2235
[21]	Mark J.E., Macromolecules, 1978, 11(4), 627—633
[22]	Flory P.J., Statistical Mechanics of Chain Molecules, Wiley,New York, 1969, 30—131
[23]	Carballeira L., Pereiras A.J., Rios M. A., Macromolecules, 1990, 23(5), 1309—1312
[24]	Tonelli A.E., Macromolecules, 1976, 9(4), 547—551
[25]	Peng J.B., He P. S., Conformational Statistical of Polymer, University of Science and Technology of China Press, Hefei, 2006, 105—123
	(彭建邦, 何平笙. 高分子链构象统计学, 合肥: 中国科学技术大学出版社, 2006, 105—123)
[26]	Yang Y.L., Hu H. J., Polymer Physics, Chemistry Industry Press, Beijing, 2001, 242—262
	(杨玉良, 胡汉杰. 高分子物理, 北京: 化学工业出版社, 2001, 242—262)
[27]	Ma H.Z., Zhang L X., Polymer Journal, 1997, 29(12), 1012—1015