Synthesis of TiCl3 Complexes Containing Aryloxy Groups and Application for Ethylene Polymerization and Copolymerization†

doi:10.7503/cjcu20170841

Abstract

Abstract:

Novel olefin polymerization catalysts with lower cost and simple synthetic process were developed. ArOTiCl₃ complexes[(2-OMeC₆H₄O)TiCl₃(C1), (2,4-Me₂C₆H₃O)TiCl₃(C2), TiCl₃(1,4-OC₆H₄O)TiCl₃(C3), TiCl₃(1,4-OC₆H₂O-Me₂-2,5)TiCl₃(C4)] and corresponding (ArO)₂TiCl₂ complexes [TiCl₂·(OC₆H₄-OMe-2)₂(C5) and TiCl₂(OC₆H₃-Me₂-2,6)₂(C6)] were synthesized and well characterized. When combined with methylaluminoxane(MAO), the ArOTiCl₃ /MAO system shows moderate activity for ethylene copolymerization with 1-hexene. The ¹³C NMR result of polymer indicates that the 1-hexene incorporation in polymer reached up to 6.88%(molar fraction). The polymer was characterized by ¹³C NMR and the mechanisms of methyl, ethyl and long side chain formation were given. The effects of polymerization temperature, concentration of polymerization monomer and polymerization time on the catalytic activity were investigated.

Key words: ArOTiCl₃ complex, Olefin polymerization catalyst, Ethylene/1-hexene copolymerization

CLC Number:

O631
O614.8

TrendMD:

WANG Jianwei, REN Yingchun, MI Puke, XU Sheng. Synthesis of TiCl₃ Complexes Containing Aryloxy Groups and Application for Ethylene Polymerization and Copolymerization^†[J]. Chem. J. Chinese Universities, 2018, 39(8): 1806.

Figures/Tables 12

References 35

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Run	Cat.	Olefin	10^-6 Activity/ (g Polymer·mol^-1·h^-1)	10^-4 M_η	10^-4M_n	10^-4M_w	PDI	Molar fraction of 1-hexene incorporation(%)
1	C1	Ethylene	2.40	23.2	2.36	22.69	9.62
2		Ethylene/1-hexene	1.50	13.3				5.59
3	C2	Ethylene	3.20	14.5
4		Ethylene/1-hexene	1.50	10.5	1.39	12.82	9.25	4.34
5	C3	Ethylene	1.60	12.9
6		Ethylene/1-hexene	0.90	3.2	0.72	3.12	4.32	4.88
7	C4	Ethylene	1.60	9.1
8		Ethylene/1-hexene	1.00	6.8	1.39	6.89	4.97	6.88
9	R3	Ethylene	0.44	10.0	1.49	10.20	6.80
10	R4	Ethylene	0.10	10.2	2.73	10.90	7.10
11	Cp₂TiCl₂	Ethylene	4.51	2.5	1.60	2.86	1.79

Run	Cat.	Olefin	10^-6 Activity/ (g Polymer·mol^-1·h^-1)	10^-4 M_η	10^-4M_n	10^-4M_w	PDI	Molar fraction of 1-hexene incorporation(%)
1	C1	Ethylene	2.40	23.2	2.36	22.69	9.62
2		Ethylene/1-hexene	1.50	13.3				5.59
3	C2	Ethylene	3.20	14.5
4		Ethylene/1-hexene	1.50	10.5	1.39	12.82	9.25	4.34
5	C3	Ethylene	1.60	12.9
6		Ethylene/1-hexene	0.90	3.2	0.72	3.12	4.32	4.88
7	C4	Ethylene	1.60	9.1
8		Ethylene/1-hexene	1.00	6.8	1.39	6.89	4.97	6.88
9	R3	Ethylene	0.44	10.0	1.49	10.20	6.80
10	R4	Ethylene	0.10	10.2	2.73	10.90	7.10
11	Cp₂TiCl₂	Ethylene	4.51	2.5	1.60	2.86	1.79

Temperature/℃	10^-6Activity/(g∙mol^-1Ti∙h^-1)
Temperature/℃	C1	C2	C3	C4
30	0.772	0.612	0.409	0.403
40	0.896	0.871	0.432	0.442
50	1.175	0.932	0.497	0.503
60	1.052	0.902	0.573	0.591
70	0.997	0.874	0.481	0.585

Temperature/℃	10^-6Activity/(g∙mol^-1Ti∙h^-1)
Temperature/℃	C1	C2	C3	C4
30	0.772	0.612	0.409	0.403
40	0.896	0.871	0.432	0.442
50	1.175	0.932	0.497	0.503
60	1.052	0.902	0.573	0.591
70	0.997	0.874	0.481	0.585

V(1-Hexene)/mL	10^-6Activity/(g∙mol^-1Ti∙h^-1)
V(1-Hexene)/mL	C1	C2	C3	C4
0	1.133	1.322	0.655	0.573
0.3	1.531	1.403	0.768	0.799
0.7	1.061	1.296	0.702	0.743
1.0	0.745	0.865	0.593	0.632
1.3	0.654	0.725	0.433	0.503
1.6	0.517	0.573	0.402	0.444

Synthesis of TiCl₃ Complexes Containing Aryloxy Groups and Application for Ethylene Polymerization and Copolymerization^†

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Time/min	10^-6Activity/(g∙mol^-1Ti∙h^-1)
Time/min	C1	C2	C3	C4
10	3.076	2.936	1.402	1.612
20	2.786	2.419	1.178	1.511
30	1.985	1.772	0.846	1.204
40	1.543	1.407	0.647	0.694
50	1.257	1.156	0.512	0.532

Molar ratio of Al/Ti	10^-6Activity/(g∙mol^-1Ti∙h^-1)
Molar ratio of Al/Ti	C1	C2	C3	C4
500	0.843	0.765	0.498	0.437
750	1.378	1.084	0.772	0.613
1000	1.599	1.537	0.93	0.907
1250	1.921	1.703	0.913	0.888
1500	1.711	1.603	0.892	0.844

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