Preparation and Characterization of Propylene/1-Butene Alloy with Bulk Copolymerization†

doi:10.7503/cjcu20140399

Abstract

Abstract:

The spherical MgCl₂ supported TiCl₄ catalyst(TiCl₄/MgCl₂/DIBP) was applied to bulk copolymerization of propylene and 1-butene. The influence of comonomer feed ratio on catalyst activity and stereoregularity of the copolymers were studied. The composition and properties of copolymers were investigated by ¹³C nuclear magnetic resonance(¹³C NMR), differential scanning calorimetry(DSC), infrared(IR) and gel permeation chromatography(GPC). The results showed that the polymerization activity increased firstly and then decreased with the increasing 1-butene/propylene feed ratio(B/P). The highest polymerization activity was achieved at B/P=0.26. As the 1-butene content in the copolymers increased, the melting point of the copolymers decreased and the molecular weight distribution became narrow. Meanwhile, the mechanical properties of the copolymers were improved significantly, and the transparency was gradually increased.

Key words: Comonomer effect, Propylene/1-butene copolymerization, Bulk polymerization

CLC Number:

O631

TrendMD:

ZHANG Chunyu, DONG Bo, ZHANG Hexin, CHEN Chunhai, ZHANG Xuequan. Preparation and Characterization of Propylene/1-Butene Alloy with Bulk Copolymerization^†[J]. Chem. J. Chinese Universities, 2014, 35(9): 2014.

Figures/Tables 8

Table 1 Copolymerization of 1-butene/propylene*

Run	Molar ratio of 1-butene/propylene	Content of 1-butene(¹³C NMR)^b(%)	10^-6 Activity/(g·g^-1Ti·h^-1)
1	0.054	0.42	1.70
2	0.12	2.04	3.97
3	0.26	4.95	4.36
4	0.30	5.61	2.71
5	0.39	6.33	2.11

Fig.1 FTIR spectra of poly(propylene-co-1-butene)s with different 1-butene feed ratios

Fig.2 13C NMR spectrum of poly(propylene-co-1-butene) with 4.95% 1-butene

Table 2 Sequence distribution of copolymers*

Run	Sequence composition											Average sequenc length
Run	P	B	PP	PB	BB	PPP	PPB	BPB	PBP	BBP	BBB	B	P
1	99.6	0.4	99.1	0.9	0	92.3	6.7	0.5	0.3	0	0	1	222
2	97.6	2.4	95.1	4.9	0	83.0	12.4	3.95	0.6	0	0	1	40.8
3	95.1	4.9	89.8	10.1	0.1	78.2	14.3	0.2	7.2	0.07	0	1	22.6
4	94.4	5.6	89.1	11.7	0.2	61.4	19.7	8.7	9.1	0.6	0.3	1	17.1
5	93.6	6.3	86.7	13.1	0.2	62.1	26.7	1.2	6.8	1.5	1.4	1	15.2

Fig.3 DSC curves of the resultant copolymers

Table 3 DSC and GPC data of copolymers with different 1-butene contents

Run	w(1-Butene) (%)	$T m *$ /℃	T_c/℃	10^-5 M_w	M_w/M_n	Run	w(1-Butene) (%)	$T m *$ /℃	T_c/℃	10^-5 M_w	M_w/M_n
1	0	165.9	112.3	4.32	3.44	4	4.95	145.1	91.0	3.11	2.30
2	0.42	163.3	107.5	3.11	2.82	5	5.61	145.8	95.0	3.41	2.25
3	2.04	156.0	99.7	3.25	2.61	6	6.33	142.6	92.5	3.13	2.86

Table 3 DSC and GPC data of copolymers with different 1-butene contents

Run	w(1-Butene) (%)	$T m *$ /℃	T_c/℃	10^-5 M_w	M_w/M_n	Run	w(1-Butene) (%)	$T m *$ /℃	T_c/℃	10^-5 M_w	M_w/M_n
1	0	165.9	112.3	4.32	3.44	4	4.95	145.1	91.0	3.11	2.30
2	0.42	163.3	107.5	3.11	2.82	5	5.61	145.8	95.0	3.41	2.25
3	2.04	156.0	99.7	3.25	2.61	6	6.33	142.6	92.5	3.13	2.86

Fig.4 Polarized optical micrographs of the copolymers with different 1-butene contents w(1-Butene)(%): (A) 0; (B) 2.04; (C) 5.61; (D) 6.33.

Table 4 Mechanical properties of copolymers with different 1-butene contents

Run	w(1-Butene)(%)	Elongation at break(%)	Impact strength/(kJ·m^-2)	Yield strength/MPa
1	0	280	1.67	41.9
2	0.43	570	1.62	37.8
3	2.04	600	1.69	44.0
4	4.95	812	2.18	35.3
5	5.61	800	2.64	31.2
6	6.33	820	2.70	30.1

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