Crystallization Kinetics of trans-/cis-Polyisoprene Blends†

doi:10.7503/cjcu20160394

Abstract

Abstract:

Isothermal and non-isothermal crystallization kinetics of cis-1,4-polyisoprene(CPI)/trans-1,4-polyisoprene(TPI) binary blends were investigated by differential scanning calorimetry method. The results were analyzed by Avrami equation and MO theory. It was found that the presence of CPI suppressed the crystallization rate of TPI component during both isothermal and non-isothermal crystallization. The crystallinity of TPI component was enhanced by CPI during the isothermal crystallization. For non-isothermal crystallization, the relative content of β crystal form increased, while the crystallinity of TPI component changed little with the incorporation of CPI component.

Key words: Polyisoprene, Binary blend, Isothermal crystallization, Non-isothermal crystallization

CLC Number:

O631.1⁺3

TrendMD:

YAO Kuncheng, NIE Huarong, MA Yunsheng, WANG Riguo, WANG Xiaojian, HE Aihua. Crystallization Kinetics of trans-/cis-Polyisoprene Blends^†[J]. Chem. J. Chinese Universities, 2016, 37(12): 2315.

Figures/Tables 11

Fig.1 DSC curves of isothermal crystallization of TPI/CPI blends at crystallization temperatures of 20 ℃(A), 25 ℃(B) and 30 ℃(C) m(TPI)∶m(CPI): a. 100∶0; b. 80∶20; c. 50∶50; d. 30∶70.

Fig.2 Relative crystallinity of TPI/CPI blends at crystallization temperatures of 20 ℃(A), 25 ℃(B) and 30 ℃(C)m(TPI)∶m(CPI): a. 100∶0; b. 80∶20; c. 50∶50; d. 30∶70.

Fig.3 Plots of lg{-ln[1-X(t)]} vs. lgt for TPI/CPI blends at crystallization temperatures of 20 ℃(A), 25 ℃(B) and 30 ℃(C)m(TPI)∶m(CPI): a. 100∶0; b. 80∶20; c. 50∶50; d. 30∶70.

Table 1 Crystallization parameters of TPI/CPI blends at different crystallization temperature

T_c/℃	m(TPI)∶m(CPI)	Δ $H c a$ /(J·g^-1)	Δ $H c, TPI a$ /(J·g^-1)	n^b	K^b	$t 12 c$ /min
20	100∶0	32.22	32.22	2.15	178.31	0.64
	80∶20	32.19	40.24	2.60	6.03	2.56
	50∶50	24.37	48.74	2.92	0.79	4.66
	30∶70	14.27	47.57	2.29	0.09	17.68
25	100∶0	39.29	39.29	2.60	31.44	1.36
	80∶20	33.28	41.60	2.83	0.61	5.34
	50∶50	24.26	48.52	2.78	0.18	8.56
	30∶70	16.50	55.00	2.01	0.06	32.50
30	100∶0	42.83	42.83	2.93	2.46	3.14
	80∶20	31.60	39.50	2.89	0.04	13.44
	50∶50	22.52	45.04	2.66	0.03	18.54
	30∶70	18.75	62.50	1.89	0.03	59.64

Table 1 Crystallization parameters of TPI/CPI blends at different crystallization temperature

T_c/℃	m(TPI)∶m(CPI)	Δ $H c a$ /(J·g^-1)	Δ $H c, TPI a$ /(J·g^-1)	n^b	K^b	$t 12 c$ /min
20	100∶0	32.22	32.22	2.15	178.31	0.64
	80∶20	32.19	40.24	2.60	6.03	2.56
	50∶50	24.37	48.74	2.92	0.79	4.66
	30∶70	14.27	47.57	2.29	0.09	17.68
25	100∶0	39.29	39.29	2.60	31.44	1.36
	80∶20	33.28	41.60	2.83	0.61	5.34
	50∶50	24.26	48.52	2.78	0.18	8.56
	30∶70	16.50	55.00	2.01	0.06	32.50
30	100∶0	42.83	42.83	2.93	2.46	3.14
	80∶20	31.60	39.50	2.89	0.04	13.44
	50∶50	22.52	45.04	2.66	0.03	18.54
	30∶70	18.75	62.50	1.89	0.03	59.64

Fig.4 DSC thermograms with different cooling rates for neat TPI and TPI/CPI blends m(TPI)∶m(CPI): (A) 100∶0; (B) 80∶20; (C) 50∶50; (D) 30∶70. Cooling rate/(℃·min-1): a. 2; b. 5; c. 10; d. 20.

Fig.5 Plots of the relative crystallinity vs. crystallization temperature for TPI/CPI blends with different cooling ratesCooling rate/(℃·min-1): a. 2; b. 5; c. 10; d. 20.m(TPI)∶m(CPI): (A) 100∶0; (B) 80∶20; (C) 50∶50.

Fig.6 Plots of the relative crystallinity vs. crystallization time for TPI/CPI blends with different cooling ratesCooling rate/(℃·min-1): a. 2; b. 5; c.10; d. 20.m(TPI)∶m(CPI): (A) 100∶0; (B) 80∶20; (C) 50∶50.

Fig.7 Plots of lnΦ vs. lnt for TPI/CPI blendsXc(%): a. 20; b. 40; c. 60; d. 80. m(TPI)∶m(CPI): (A) 100∶0; (B) 80∶20; (C) 50∶50.

Table 2 Kinetic parameters for non-isothermal crystallization of TPI/CPI blends*

m(TPI)∶m(CPI)	X_c = 20%		X_c=40%		X_c=60%		X_c=80%
m(TPI)∶m(CPI)	F(T)	a	F(T)	a	F(T)	a	F(T)	a
100∶0	11.87	1.48	14.34	1.42	16.35	1.40	18.81	1.38
80∶20	12.05	1.17	14.40	1.18	16.36	1.19	18.73	1.21
50∶50	23.27	1.51	28.79	1.49	33.92	1.49	41.34	1.50

Fig.8 DSC heating curves with a heating rate of 10 ℃/min for TPI/CPI blendsHeating rate/(℃·min-1): a. 2; b. 5; c.10; d. 20. m(TPI)∶m(CPI): (A) 100∶0; (B) 80∶20; (C) 50∶50.

Table 3 Values of melting enthalpy for non-isothermal crystallization of TPI/CPI blends

Heating rate/(℃·min^-1)	m(TPI)∶m(CPI)	Δ $H f *$ /(J·g^-1)	Δ $H f, TPI *$ /(J·g^-1)
2	100∶0	49.17	49.17
	80∶20	37.22	46.53
	50∶50	22.77	45.54
5	100∶0	44.60	44.6
	80∶20	34.35	42.94
	50∶50	22.31	44.62
10	100∶0	42.16	42.16
	80∶20	33.39	41.74
	50∶50	21.54	43.08
20	100∶0	40.83	40.83
	80∶20	33.30	41.63
	50∶50	21.38	42.76

Table 3 Values of melting enthalpy for non-isothermal crystallization of TPI/CPI blends

Heating rate/(℃·min^-1)	m(TPI)∶m(CPI)	Δ $H f *$ /(J·g^-1)	Δ $H f, TPI *$ /(J·g^-1)
2	100∶0	49.17	49.17
	80∶20	37.22	46.53
	50∶50	22.77	45.54
5	100∶0	44.60	44.6
	80∶20	34.35	42.94
	50∶50	22.31	44.62
10	100∶0	42.16	42.16
	80∶20	33.39	41.74
	50∶50	21.54	43.08
20	100∶0	40.83	40.83
	80∶20	33.30	41.63
	50∶50	21.38	42.76

References 16

[1]	Bhowmick A. K., Kuo C. C., Manzur A., Arthur A. M., Intyre D. M., J. Macromol. Sci. Part B: Phys., 1986, 25(3), 283—309
[2]	Carter A.J., Davies C. K. L., Thomas A. G., Paper Presented at the First Italian-Polish Seminar on Multicomponent Polemeric Systems, Plenum Press, NewYork, 1979
[3]	Song J. S., Huang B. C., Yu D. S., J. Appl. Polym. Sci., 2001, 82(2), 81—89
[4]	Bunn C. W., Proc. R. Soc. Lond. Ser. A, 1942, 180(980), 40—66
[5]	Mandelkern L., Quinn F. A., Roberts D. E., J. Am. Chem. Soc., 1956, 78(5), 926—932
[6]	Fischer E., Henderson J. F., J. Polym. Sci. Part A, 1967, 5(2), 377—390
[7]	Candia F. D., Romano G., Taglialatela A., Vittoria V., Polym. Bull., 1981, 4(4), 233—240
[8]	Baboo M., Dixit M., Sharma K., Saxena N. S., Polym. Bull., 2011, 66(5), 661—672
[9]	Cooper W., Vaughan G., Polymer, 1962, 4, 329—340
[10]	Yao K. C., Nie H. Y., Liang Y. R., Qiu D., He A. H., Polymer, 2015, 80, 259—264
[11]	Avrami M., J. Chem. Phys., 1939, 7(12), 1103—1112
[12]	Liu T. X., Mo Z. S., Wang S. G., Zhang H. F., Polym. Eng. Sci., 1997, 37(3), 568—575
[13]	Liu L., Wang B. X., Wang Y. R., China Synthetic Rubber Industry, 2012, 35(6), 433—436
	(刘莉, 王炳昕, 王韵然. 合成橡胶工业,2012, 35(6), 433—436)
[14]	Lovering E. G., Wooden D. C., J. Polym. Sci. Part A-2, 1969, 7(10), 1639—1649
[15]	Ratri P. J., Tashiro K., Iguchi M., Polymer, 2012, 53, 3548—3558
[16]	Takahashi Y., Sato T., Tadokoro H., J. Polym. Sci. Part B, 1973, 11(2), 233—248