Fractionation and Fraction Characterization of trans-Polyisoprene Rubber Alloys within Reactor†

doi:10.7503/cjcu20180151

Abstract

Abstract:

Trans-1,4-polyisoprene rubber alloys(TPIR) with different butadiene incorporation catalyzed by supported titanium Ziegler-Natta catalyst within pilot plant reactor were effectively fractionated by the stepwise isothermal crystallization fractionation method. The microstructure, molecular weight(M_w) and molecular weight distribution(M_w/M_n), butadiene unit content($\bar{F}_{Bd}$), crystallization behavior and crystal form of main fractions were analyzed by ¹³C NMR, GPC, DSC and XRD. The results showed that trans-1,4-polyisoprene rubber alloys were mainly composed of 7 fractions(A—G). TPIR-05 with low butadiene incorporation was mainly composed of fraction C, D, G; TPIR-10 with high butadiene incorporation was mainly composed of fraction A, B, C, D, G. Fraction A having high butadiene unit content($\bar{F}_{Bd}$=22.4%, molar fraction) was gradient multi-block trans-1,4-poly(isoprene-co-butadiene) copolymers containing trans-1,4-polyisoprene(TPI) blocks and trans-1,4-polybutadiene(TPB) blocks; Fractions B, D were gradient trans-1,4-poly-(isoprene-co-butadiene) copolymers with low butadiene unit content($\bar{F}_{Bd}$=2.7%—6.5%) and long TPI blocks; fractions C were trans-1,4-polyisoprene homopolymers; fraction G were random trans-1,4-poly-(isoprene-co-butadiene) copolymers with high butadiene unit content($\bar{F}_{Bd}$=15.6%—20.4%) and weak crystallizability. The possible chain structure models for these fractions were proposed.

Key words: trans-1,4-Polyisoprene rubber alloy, Isothermal crystallization fractionation, Structure characterization, Chain structure model

CLC Number:

O632

TrendMD:

NIU Qingtao,ZOU Chen,WANG Riguo,LI Lange,HE Aihua. Fractionation and Fraction Characterization of trans-Polyisoprene Rubber Alloys within Reactor^†[J]. Chem. J. Chinese Universities, 2018, 39(10): 2312.

Figures/Tables 8

Scheme 1 Diagram of stepwise isothermal crystallization fractionation process for TPIR alloy

Table 1 Fractionation results of TPIR-05 and TPIR-10

Sample run	$F ˉ Bd$ (%, molar fraction)	Mass fraction(%)
Sample run	$F ˉ Bd$ (%, molar fraction)	A(>80 ℃)	B(20 ℃)	C(10 ℃)	D(0 ℃)	E(-10 ℃)	F(-20 ℃)	G(<20 ℃)
TPIR-05	4.8	1.3	3.9	24.4	47.2	8.4	2.0	12.8
TPIR-10	10.5	31.8	14.4	26.4	7.9	2.0	2.6	11.9

Table 1 Fractionation results of TPIR-05 and TPIR-10

Sample run	$F ˉ Bd$ (%, molar fraction)	Mass fraction(%)
Sample run	$F ˉ Bd$ (%, molar fraction)	A(>80 ℃)	B(20 ℃)	C(10 ℃)	D(0 ℃)	E(-10 ℃)	F(-20 ℃)	G(<20 ℃)
TPIR-05	4.8	1.3	3.9	24.4	47.2	8.4	2.0	12.8
TPIR-10	10.5	31.8	14.4	26.4	7.9	2.0	2.6	11.9

Table 2 Summary of fraction butadiene unit content and microstructure

Fraction	Mass fraction(%)	$F ˉ Bd *$ (%)	Molar fraction of microstructure^*(%)
			Ip unit			Bd unit
			trans-1,4	cis-1,4	3,4-	trans-1,4	cis-1,4	1,2-
TPIR-05-B	3.9	3.3	96.7	3.1	1.2	99.6	0	0.4
TPIR-05-C	24.4	0.5	99.0	0.9	0.1	98.1	0.2	1.7
TPIR-05-D	47.2	2.7	98.1	1.7	0.2	99.6	0.1	0.3
TPIR-05-F	2.0	9.2	97.3	2.4	0.3	98.7	0.8	0.5
TPIR-05-G	12.8	15.6	89.1	10.6	0.3	97.3	2.6	0.2
TPIR-10-A	31.8	22.4	99.6	0.4	0	99.6	0.2	0.2
TPIR-10-B	14.4	6.5	94.6	4.0	1.4	97.1	2.1	0.8
TPIR-10-C	26.4	3.2	97.2	1.6	1.1	99.0	0.4	0.7
TPIR-10-E	2.0	7.7	99.4	0.1	0.5	99.8	0.1	0.1
TPIR-10-G	11.9	20.4	89.5	10.3	0.2	98.7	1.1	0.1

Table 2 Summary of fraction butadiene unit content and microstructure

Fraction	Mass fraction(%)	$F ˉ Bd *$ (%)	Molar fraction of microstructure^*(%)
			Ip unit			Bd unit
			trans-1,4	cis-1,4	3,4-	trans-1,4	cis-1,4	1,2-
TPIR-05-B	3.9	3.3	96.7	3.1	1.2	99.6	0	0.4
TPIR-05-C	24.4	0.5	99.0	0.9	0.1	98.1	0.2	1.7
TPIR-05-D	47.2	2.7	98.1	1.7	0.2	99.6	0.1	0.3
TPIR-05-F	2.0	9.2	97.3	2.4	0.3	98.7	0.8	0.5
TPIR-05-G	12.8	15.6	89.1	10.6	0.3	97.3	2.6	0.2
TPIR-10-A	31.8	22.4	99.6	0.4	0	99.6	0.2	0.2
TPIR-10-B	14.4	6.5	94.6	4.0	1.4	97.1	2.1	0.8
TPIR-10-C	26.4	3.2	97.2	1.6	1.1	99.0	0.4	0.7
TPIR-10-E	2.0	7.7	99.4	0.1	0.5	99.8	0.1	0.1
TPIR-10-G	11.9	20.4	89.5	10.3	0.2	98.7	1.1	0.1

Table 3 Summary of fraction characterization

Fraction	Dyad sequence^a(%)			$n ˉ Ip a$	$n ˉ Bd a$	10^-5 $M w b$	M_w/ $M n b$	$T g c$ /℃	$X c d$ (%)
Fraction	[II]	[BI]+[IB]	[BB]	$n ˉ Ip a$	$n ˉ Bd a$	10^-5 $M w b$	M_w/ $M n b$	$T g c$ /℃	$X c d$ (%)
TPIR-05-B	95.1	3.1	1.8	62.5	2.2	-	-	-67.4
TP IR-05-C	99.1	0.8	0.1	253.4	1.2	4.4	5.7	-66.5
TPIR-05-D	96.4	1.9	1.7	101.7	1.8	4.5	5.8	-66.9
TPIR-05-F	82.7	16.2	1.1	11.2	1.1	3.4	3.4	-69.0
TPIR-05-G	70.9	23.1	6.0	7.1	1.5	4.0	4.8	-73.9	6.5
TPIR-10-A	69.1	16.9	14.0	9.2	2.6		-	-69.6	11.3
TPIR-10-B	89.3	8.4	2.3	22.3	1.6	5.9	4.0	-71.2	11.8
TPIR-10-C	96.3	1.0	2.7	187.5	2.2	2.7	4.3	-	12.5
TPIR-10-E	89.3	6.0	4.7	31.0	2.1	6.9	3.9	-68.2
TPIR-10-G	62.8	33.5	3.7	4.8	1.2	6.6	4.4	-74.5	5.6

Table 3 Summary of fraction characterization

Fraction	Dyad sequence^a(%)			$n ˉ Ip a$	$n ˉ Bd a$	10^-5 $M w b$	M_w/ $M n b$	$T g c$ /℃	$X c d$ (%)
Fraction	[II]	[BI]+[IB]	[BB]	$n ˉ Ip a$	$n ˉ Bd a$	10^-5 $M w b$	M_w/ $M n b$	$T g c$ /℃	$X c d$ (%)
TPIR-05-B	95.1	3.1	1.8	62.5	2.2	-	-	-67.4
TP IR-05-C	99.1	0.8	0.1	253.4	1.2	4.4	5.7	-66.5
TPIR-05-D	96.4	1.9	1.7	101.7	1.8	4.5	5.8	-66.9
TPIR-05-F	82.7	16.2	1.1	11.2	1.1	3.4	3.4	-69.0
TPIR-05-G	70.9	23.1	6.0	7.1	1.5	4.0	4.8	-73.9	6.5
TPIR-10-A	69.1	16.9	14.0	9.2	2.6		-	-69.6	11.3
TPIR-10-B	89.3	8.4	2.3	22.3	1.6	5.9	4.0	-71.2	11.8
TPIR-10-C	96.3	1.0	2.7	187.5	2.2	2.7	4.3	-	12.5
TPIR-10-E	89.3	6.0	4.7	31.0	2.1	6.9	3.9	-68.2
TPIR-10-G	62.8	33.5	3.7	4.8	1.2	6.6	4.4	-74.5	5.6

Fig.1 G fractions characterization (A) 13C NMR spectra; (B) WAXD patterns; (C) the second heating scan of DSC curves; (D) the cooling DSC curves.

Fig.2 Fraction characterization of B, C, D(A) 13C NMR spectra; (B) GPC curves; (C) the second heating scan of DSC curves; (D) the cooling DSC curves.

Fig.3 Fraction characterization of A(TPIR-10-A) (A) 13C NMR spectrum; (B) XRD pattern; (C) DSC curve.

Table 4 Chain structure model of fractions

References 34

[1]	Galli P., Vecellio G., Prog. Polym. Sci., 2001, 26(8), 1287—1336
[2]	Sionkowska A., Prog. Polym. Sci., 2011, 36(9), 1254—1276
[3]	Xue L.J., Zhang J. L., Han Y. C., Prog. Polym. Sci., 2012, 37(5), 564—594
[4]	Song J.S., Huang B. C., Yu D. S., J. Appl. Polym. Sci., 2001, 82(1), 81—89
[5]	Feng Y.H., Song J. S., Huang B. C., Chin. Synth. Rubb. Ind., 1999, 22(5), 276—280
[6]	Niu Q.T., Jiang X. B., He A. H., Polymer, 2014, 55(9), 2146—2152
[7]	Mandelkern L., Quinn F.A., Roberts D. E., J. Am. Chem. Soc., 1956, 78(5), 926—932
[8]	Yao K.C., Nie H. R., Liang Y. R., Qiu D., He A. H., Polymer, 2015, 80, 259—264
[9]	Wang H., Song L.Y., Ma R. S., Wang R. G., He A. H., Acta Polym. Sin., 2018, (3), 1—10
[10]	Zhang X.H., Cui H. H., Song L. Y., Ren H. C., Wang R. G., He A. H., Composites Science and Technology, 2018, 158, 156—163
[11]	He A.H., Huang B. C., Jiao S. K., Hu Y. L., J. Appl. Polym. Sci., 2003, 89(7), 1800—1807
[12]	He A.H., Yao W., Huang B. C., Huang Y. Q., Jiao S. K., J. Appl. Polym. Sci., 2004, 92(5), 2941—2948
[13]	Wang H., Zhang J.P., Ma Y. S., Wang R. G., He A. H., Chem. J. Chinese Universities, 2017, 38(11), 2095—2101
	(王浩, 张剑平, 马韵升, 王日国, 贺爱华. 高等学校化学学报, 2017, 38(11), 2095—2101)
[14]	Wang H., Song L.Y., Zhang J. P., Wang R. G., He A. H., Petrochemical Technology, 2017, 46(6), 744—750
[15]	Zhang Z.Q., Cui L., Yao W., J. Qingdao Unin. Sci. Technol., 2012, 33(4), 396—404
[16]	Wang H., Cui H.H., Wang R. G., Xu X. J., He A. H., Chin. Synth. Rubb. Ind., 2017, 40(1), 12—17
[17]	Jiang X.B., Zhang Q. F., He A. H., Chin. J. Polym. Sci., 2015, 33(6), 815—822
[18]	He A.H., Yao W., Huang B. C., Jiao S. K., Acta Chim. Sin., 2001, 59, 1793—1797
[19]	Lodefier P., Jonas A.M., Legras R., Macromolecules, 1999, 32(21), 7135—7139
[20]	Ramachandran R., Beaucage G., Mcfaddin D., Merrick-Mack J., Galiatsatos V., Mirabella F., Polymer, 2011, 52, 2661—2666
[21]	Monrabal B., J. Appl. Polym. Sci., 1994, 52(4), 491—499
[22]	Anantawaraskul S., Soares J.B. P., Wood-Adams P. M., Monrabal B., Polymer, 2003, 44, 2393—2401
[23]	Monrabal B., Sancho-Tello J., Mayo N., Romero L., Macromol. Symp., 2007, 257(1), 71—79
[24]	Cong R J., Groot W.D., Parrott A., Yau W., Hazlitt L., Brown R., Miller M., Zhou Z., Macromolecules, 2011, 44(8), 3062—3072
[25]	Cheruthazhekatt S., Pijpers T.F. J., Harding G. W., Mathot V. B. F., Pasch H., Macromolecules, 2012, 45(12), 5866—5880
[26]	Yau W.W., Gillespie D., Polymer, 2001, 42, 8947—8958
[27]	Xu J.T., Feng L. X., Yang S. L., Macromolecules, 1997, 30(9), 2539—2541
[28]	Muller A.J., Arnal M. L., Prog. Polym. Sci., 2005, 30(5), 559—603
[29]	Niu Q.T., Zou C., Liu X. Y., Wang R. G., He A. H., Polymer, 2017, 109, 197—204
[30]	Lobach M.I., Poletayeva I. A., Khatchaturov A. S., Druz N. N., Kormer V. A., Polymer, 1977, 18, 1196—1198
[31]	Guo C.L., Zhou Z. N., Gong Z., Acta Polym. Sin., 1991, (1), 77—83
[32]	China Petroleum and Chemical Indusrty Association , GB/T 1232GB/T 1232.1-2000 Unvulcanized Rubber Determination by a Disc Shear Viscometer Part One: Determination of Mooney Viscosity, Beijing: China Standards Press, 2004-03-29
	(中国石油和化学工业协会. GB/T 1232.1-2000 未硫化橡胶, 用圆盘剪切黏度计进行测定, 第1部分: 门尼黏度的测定, 北京: 中国标准出版社, 2004-03-29)
[33]	Mandelkern L., Quinn F.A., Roberts D. E., J. Am. Chem. Soc., 1956, 78(5), 926—932
[34]	Sun X.H., Ni X. Y., J. Appl. Polym. Sci., 2004, 94(6), 2286—2294