Copolymerization of Norbornene and 1-Octene Catalyzed by Bis(phenoxy-imine) Titanium Complex†

doi:10.7503/cjcu20180089

Abstract

Abstract:

The copolymer of norbornene with 1-octene was prepared by the catalysis of the ternary catalytic system consisted of bis(phenoxy-imine) titanium complex(Ti), triisobutyl aluminum(Al) and organoboron compound(B). The obtained copolymer showed a modest molecular weight(M_w: ca. 3.0×10⁴—6.5×10⁴) and broad molecular weight distribution(MWD: ca. 2.0). The influence of copolymerization conditions was explored. The optimal copolymerization conditions are as follows: n(Al)/n(Ti)=5:1, n(B)/n(Ti)=1:1, n(Monomer)/n(Ti)=400:1, n(NBE)/n(OC)=5:5, polymerized at 40 ℃ for 6 h and the copolymer yield reached up to 43.7%. The reactivity ratios of norbornene and 1-octene were 3.01 and 0.08, respectively, tending to form a random copolymer. The copolymer exhibited good thermal stability(T_d>300 ℃) and moderate glass transition temperature(T_g=87—174 ℃) controlled by the content of norbornene in the backbone.

Key words: Bis(phenoxy-imine) titanium complex, Norbornene, 1-Octene, Random copolymer, Thermal stability

CLC Number:

O632.1

TrendMD:

MENG Jiafeng, NI Xufeng, ZHENG Hao, SHEN Zhiquan. Copolymerization of Norbornene and 1-Octene Catalyzed by Bis(phenoxy-imine) Titanium Complex^†[J]. Chem. J. Chinese Universities, 2018, 39(8): 1853.

Figures/Tables 8

Table 1 Copolymerization of NBE with OC catalyzed by 1/TIBA/B ternary systema

Sample	n(Al)/n(Ti)	n(NBE)/n(OC)	Polymerization time/h	Yield(%)	10^-4 $M w b$	PDI^b	$f NBE c$ (%)
NOC-1	5:1	0:10	6	14.4	239/1.43	1.38/1.52
NOC-2	3:1	5:5	6	14.6	6.46	1.91	73.4
NOC-3	10:1	5:5	6	39.7	3.00	2.22	57.5
NOC-4^d	5:1	5:5	6	31.6	4.84	2.45	63.7
NOC-5	5:1	5:5	6	43.7	4.70	2.08	60.6
NOC-6^e	5:1	5:5	6	37.4	4.22	1.97	62.5
NOC-7	5:1	1:9	6	20.2	1.30	2.23	31.9
NOC-8	5:1	3:7	6	28.2	3.78	2.24	53.5
NOC-9	5:1	5:5	4	42.8	5.51	2.36	61.0
NOC-10	5:1	5:5	2	38.0	4.85	2.27	63.3
NOC-11	5:1	5:5	1	30.6	4.91	2.36	64.5
NOC-12	5:1	5:5	0.5	18.7	3.37	1.94	68.5

Table 1 Copolymerization of NBE with OC catalyzed by 1/TIBA/B ternary systema

Sample	n(Al)/n(Ti)	n(NBE)/n(OC)	Polymerization time/h	Yield(%)	10^-4 $M w b$	PDI^b	$f NBE c$ (%)
NOC-1	5:1	0:10	6	14.4	239/1.43	1.38/1.52
NOC-2	3:1	5:5	6	14.6	6.46	1.91	73.4
NOC-3	10:1	5:5	6	39.7	3.00	2.22	57.5
NOC-4^d	5:1	5:5	6	31.6	4.84	2.45	63.7
NOC-5	5:1	5:5	6	43.7	4.70	2.08	60.6
NOC-6^e	5:1	5:5	6	37.4	4.22	1.97	62.5
NOC-7	5:1	1:9	6	20.2	1.30	2.23	31.9
NOC-8	5:1	3:7	6	28.2	3.78	2.24	53.5
NOC-9	5:1	5:5	4	42.8	5.51	2.36	61.0
NOC-10	5:1	5:5	2	38.0	4.85	2.27	63.3
NOC-11	5:1	5:5	1	30.6	4.91	2.36	64.5
NOC-12	5:1	5:5	0.5	18.7	3.37	1.94	68.5

Fig.1 Relationship of copolymeriation time and copolymer yield catalyzed by 1/TIBA/B

Scheme 1 Assumed mechanism for the copolymerization of norbornene with 1-octene

Fig.2 Linear fitting of the NBE/OC copolymerization system catalyzed by 1/TIBA/B according to Kelen-Tυ¨dós method

Fig.3 GPC curve of copolymer NOC-5

Fig.4 1H NMR(A) and 13C NMR(B) spectra of copolymer NOC-5

Fig.5 DSC curves of copolymer NOC-7(a),NOC-8(b) and NOC-5(c)

Fig.6 TGA curves of copolymer NOC-7(a),NOC-8(b) and NOC-5(c)

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