Copolymerization of Norbornene and n-Butyl Methacrylate Catalyzed by Novel Ni(Ⅱ)(benzocyclohexan-ketoarylimino) 2 †

doi:10.7503/cjcu20140932

Abstract

Abstract:

Vinyl-addition copolymerization of norbornene(NB) and polar monomer n-butyl methacrylate(n-BMA) were carried out via two novel high activity catalysts, Ni(Ⅱ)(benzocyclohexan-ketoarylimino)₂(Ni{C₁₀H₈(O)C[2,6-C₆H₃(CH₃)₂N]CH₃}₂, C1) and Ni{C₁₀H₈(O)C[2,6-C₆H₃Cl₂N]CH₃}₂, C2), in combination with tris(pentafluorophenyl)-borance[B(C₆F₅)₃]. A possible catalytic deactivation mechanism of polymerization was presented. Influence of monomer feed ratio on catalytic activity, conversion rate and properties of outcomes were investigated. Reactivity ratios of co-monomers were estimated by Kelen-Tüdõs method, they are r_n_-BMA=0.02, r_NB=16.28, r_NB·r_n_-BMA=0.32 for C1/B(C₆F₅)₃catalytic system, and r_n_-BMA=0.01, r_NB=64.83, r_NB·r_n_-BMA=0.65 for C2/B(C₆F₅)₃ catalytic system. These indicate the random copolymerization of NB/n-BMA occurs with both C1/B(C₆F₅)₃ and C2/B(C₆F₅)₃.

Key words: Nickel complex, Norbornene, n-Butyl methacrylate, Reactivity ratio, Addition copolymerization

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TrendMD:

HE Xiaohui, LIU Jingyin, CHEN Lu, ZHU Hongyu, WANG Juan. Copolymerization of Norbornene and n-Butyl Methacrylate Catalyzed by Novel Ni(Ⅱ)(benzocyclohexan-ketoarylimino)₂ ^†[J]. Chem. J. Chinese Universities, 2015, 36(3): 575.

Figures/Tables 9

Scheme 1 Copolymerization of NB/n-BMA catalyzed by C1/B(C6F5)3 or C2/B(C6F5)3 catalystic system

Table 1 Copolymerizations of NB/n-BMA catalyzed by C1/B(C6F5)3 and C2/B(C6F5)3 systemsa

Cat.	n(NB)/n(n-BMA)	Yield(%)	10^-5Activity/ (g_polymer·mo $l Ni - 1$ ·h^-1)	$M w b$	M_w/ $M n b$	Molar fraction of n-BMA in copolymers^c(%)
C1	100/0	79.20	2.98	Insoluble	$d$	0
C1	80/20	42.35	1.75	3.61×10⁴	1.10	3.82
C1	60/40	26.44	1.19	$d$	$d$	4.35
C1	50/50	9.54	0.45	2.97×10⁴	1.13	5.60
C2	100/0	73.10	2.75	Insoluble	$d$	0
C2	80/20	41.88	1.73	3.11×10⁴	1.14	0.33
C2	60/40	23.79	1.07	$d$	$d$	0.68
C2	50/50	9.17	0.43	3.31×10⁴	1.07	1.20

Table 1 Copolymerizations of NB/n-BMA catalyzed by C1/B(C6F5)3 and C2/B(C6F5)3 systemsa

Cat.	n(NB)/n(n-BMA)	Yield(%)	10^-5Activity/ (g_polymer·mo $l Ni - 1$ ·h^-1)	$M w b$	M_w/ $M n b$	Molar fraction of n-BMA in copolymers^c(%)
C1	100/0	79.20	2.98	Insoluble	$d$	0
C1	80/20	42.35	1.75	3.61×10⁴	1.10	3.82
C1	60/40	26.44	1.19	$d$	$d$	4.35
C1	50/50	9.54	0.45	2.97×10⁴	1.13	5.60
C2	100/0	73.10	2.75	Insoluble	$d$	0
C2	80/20	41.88	1.73	3.11×10⁴	1.14	0.33
C2	60/40	23.79	1.07	$d$	$d$	0.68
C2	50/50	9.17	0.43	3.31×10⁴	1.07	1.20

Scheme 2 Mechanism of deactivation on copolymerization of NB/n-BMA catalyzed by C1/B(C6F5)3 or C2/B(C6F5)3 catalytic system

Fig.1 GPC curves for NB/n-BMA copolymers with Mw=3.61×104(a), Mw=2.97×104(b), Mw=3.11×104(c) and Mw=3.31×104(d) obtained by C1/B(C6F5)3(a, b) and C2/B(C6F5)3(c, d) catalytic systems

Table 2 Copolymerization of NB/n-BMA catalyzed by C1/B(C6F5)3 and C2/B(C6F5)3 catalytic systems

Cat.	Molar fraction of n-BMA in the feed(%)	Molar fraction of n-BMA in copolymers^a(%)	Yield^b(%)	Polymerization time/min
C1	50	5.60	9.54	30
C1	60	7.27	7.69	30
C1	70	11.15	2.95	25
C1	80	22.60	1.45	25
C1	90	27.30	0.51	40
C2	50	1.20	9.17	30
C2	60	2.25	4.42	30
C2	70	2.69	2.36	25
C2	80	3.79	1.38	25
C2	90	6.54	0.48	40

Fig.2 Linear fitting of the NB/n-BMA copolymerization’s system catalyzed by C1/B(C6F5)3(A) and C2/B(C6F5)3(B) systems according to Kelen-Tüdõs method

Fig.3 FTIR spectra of NB/n-BMA copolymers with 0(a), 3.82%(b), 5.60%(c), 0.33%(d), 1.20%(e) of n-BMA molar ratio obtained by C1/B(C6F5)3(a–c) and C2/B(C6F5)3(d, e) catalytic systems

Fig.4 1H NMR spectra of NB/n-BMA copolymers with 7.27%(a) and 22.60%(b) of n-BMA molar ratio obtained by C1/B(C6F5)3 catalytic system

Fig.5 TGA curves of NB/n-BMA copolymers with 100%(a), 4.35%(b), 3.82%(c), 0(g) n-BMA molar ratio obtained by C1/B(C6F5)3 system and 0.33%(d), 0.68%(e), 0(f) of n-BMA molar ratio obtained by C2/B(C6F5)3 system

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Copolymerization of Norbornene and n-Butyl Methacrylate Catalyzed by Novel Ni(Ⅱ)(benzocyclohexan-ketoarylimino)₂ ^†

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