Silylene/Organoaluminum Lewis Pair System and the Initiation Property for Polymerization of (Meth)acrylates

doi:10.6023/cjoc202305019

Abstract

The initiation polymerization property of (meth)acrylates by using the silylene/organoaluminum Lewis pair (LP) system is studied. Four silylenes L(Ph₂P)Si (Si-1, L=PhC(N^tBu)₂), L[4-MeC₆H₄(Ph₂P)N]Si (Si-2), L[2,6-ⁱPr₂C₆H₃(1,5- C₈H₁₄B)N]Si (Si-3), and L(LSi)Si (Si-4) as the Lewis base (LB) were synthesized, together with six organoaluminums Al(C₆F₅)₃, AlMe(BHT)₂, AlⁱBu(BHT)₂, AlⁱBu₂(BHT), AlⁱBu(BHT^*)₂, and AlⁱBu₂(BHT^*) (BHT=2,6-^tBu₂-4-MeC₆H₂O and BHT^*=2,4,6-^tBu₃C₆H₂O) as the Lewis acid (LA). Si-1/organoaluminum and Si-4/organoaluminum LP systems all enable to initiate the complete methacrylate (MMA) polymerization, achieving turnover of frequency (TOF) activities in the range of 50~400 h^-1 with PMMA M_n of 82000~271000 and Đ of 1.11~1.81. Neither Si-2/organoaluminum or Si-3/organoaluminum was active. The Si-1/Al(C₆F₅)₃ displayed poor reactivity on n-butyl acrylate (nBA) and 2-ethylhexyl acrylate (EHA). However, the Si-1/other organoaluminums exhibited both complete nBA and EHA polymerizations. For nBA, the TOFs were obtained by 4.8×10⁴~14.4×10⁴ h^-1, in which the PnBAs were produced with M_n100000~179000 and Đ 1.08~1.59. For EHA, the TOFs were up to 14.4×10⁴~36.0×10⁴ h^-1, where the PEHAs were yielded with M_n 81000~240000 and Đ 1.12~1.95. The probable polymerization mechanism with the silylene/organoaluminum LP system is investigated.

Key words: silylene as the Lewis base, organoaluminum as the Lewis acid, Lewis pair polymerization, (meth)acrylate monomer, poly(meth)acrylates

Cite this article

Yiling Zhao, Zhikang Chen, Lei Li, Conglei Liu, Hongping Zhu. Silylene/Organoaluminum Lewis Pair System and the Initiation Property for Polymerization of (Meth)acrylates[J]. Chinese Journal of Organic Chemistry, 2023, 43(10): 3590-3597.

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Entry	LB	LA	M	M/LA/LB	t/h	M_n^b	Ð^b	I^{ c}*/%
1	Si-1	Al(C₆F₅)₃	MMA	200/2/1	3.0	82000	1.33	24.4
2	Si-1	AlMe(BHT)₂	MMA	200/2/1	1.0	152000	1.47	13.2
3	Si-1	AlⁱBu(BHT)₂	MMA	200/2/1	4.0	122000	1.31	16.4
4	Si-1	AlⁱBu₂(BHT)	MMA	200/2/1	0.5	107000	1.68	18.7
5	Si-1	AlⁱBu(BHT^*)₂	MMA	200/2/1	3.0	174000	1.11	11.5
6	Si-1	AlⁱBu₂(BHT^*)	MMA	200/2/1	2.0	124000	1.66	16.1
7	Si-4	Al(C₆F₅)₃	MMA	200/2/1	2.0	85000	1.81	23.5
8	Si-4	AlMe(BHT)₂	MMA	200/2/1	3.0	138000	1.77	14.5
9	Si-4	AlⁱBu(BHT)₂	MMA	200/2/1	3.0	134000	1.56	14.9
10	Si-4	AlⁱBu₂(BHT)	MMA	200/2/1	2.0	174000	1.67	11.5
11	Si-4	AlⁱBu(BHT^*)₂	MMA	200/2/1	3.0	202000	1.74	9.9
12	Si-4	AlⁱBu₂(BHT^*)	MMA	200/2/1	3.0	271000	1.31	7.4

Entry	LB	LA	M	M/LA/LB	t/h	M_n^b	Ð^b	I^{ c}*/%
1	Si-1	Al(C₆F₅)₃	MMA	200/2/1	3.0	82000	1.33	24.4
2	Si-1	AlMe(BHT)₂	MMA	200/2/1	1.0	152000	1.47	13.2
3	Si-1	AlⁱBu(BHT)₂	MMA	200/2/1	4.0	122000	1.31	16.4
4	Si-1	AlⁱBu₂(BHT)	MMA	200/2/1	0.5	107000	1.68	18.7
5	Si-1	AlⁱBu(BHT^*)₂	MMA	200/2/1	3.0	174000	1.11	11.5
6	Si-1	AlⁱBu₂(BHT^*)	MMA	200/2/1	2.0	124000	1.66	16.1
7	Si-4	Al(C₆F₅)₃	MMA	200/2/1	2.0	85000	1.81	23.5
8	Si-4	AlMe(BHT)₂	MMA	200/2/1	3.0	138000	1.77	14.5
9	Si-4	AlⁱBu(BHT)₂	MMA	200/2/1	3.0	134000	1.56	14.9
10	Si-4	AlⁱBu₂(BHT)	MMA	200/2/1	2.0	174000	1.67	11.5
11	Si-4	AlⁱBu(BHT^*)₂	MMA	200/2/1	3.0	202000	1.74	9.9
12	Si-4	AlⁱBu₂(BHT^*)	MMA	200/2/1	3.0	271000	1.31	7.4

Entry	LA	M	t/s	Conv.^b/%	M_n^c	Ð^c	I^d*/%
1	Al(C₆F₅)₃	nBA	60	50	—	—	—
2	AlMe(BHT)₂	nBA	5	>99	113000	1.08	17.7
3	AlⁱBu(BHT)₂	nBA	10	>99	115000	1.31	17.4
4	AlⁱBu₂(BHT)	nBA	15	>99	130000	1.54	15.4
5	AlⁱBu(BHT^*)₂	nBA	10	>99	179000	1.36	11.2
6	AlⁱBu₂(BHT^*)	nBA	5	>99	100000	1.59	20.0
7	Al(C₆F₅)₃	EHA	60	66.7	—	—	—
8	AlMe(BHT)₂	EHA	2	>99	156000	1.10	12.8
9	AlⁱBu(BHT)₂	EHA	5	>99	157000	1.12	12.7
10	AlⁱBu₂(BHT)	EHA	2	>99	240000	1.52	8.3
11	AlⁱBu(BHT^*)₂	EHA	5	>99	120000	1.66	16.7
12	AlⁱBu₂(BHT^*)	EHA	5	>99	224000	1.63	8.9

Entry	LA	M	t/s	Conv.^b/%	M_n^c	Ð^c	I^d*/%
1	Al(C₆F₅)₃	nBA	60	50	—	—	—
2	AlMe(BHT)₂	nBA	5	>99	113000	1.08	17.7
3	AlⁱBu(BHT)₂	nBA	10	>99	115000	1.31	17.4
4	AlⁱBu₂(BHT)	nBA	15	>99	130000	1.54	15.4
5	AlⁱBu(BHT^*)₂	nBA	10	>99	179000	1.36	11.2
6	AlⁱBu₂(BHT^*)	nBA	5	>99	100000	1.59	20.0
7	Al(C₆F₅)₃	EHA	60	66.7	—	—	—
8	AlMe(BHT)₂	EHA	2	>99	156000	1.10	12.8
9	AlⁱBu(BHT)₂	EHA	5	>99	157000	1.12	12.7
10	AlⁱBu₂(BHT)	EHA	2	>99	240000	1.52	8.3
11	AlⁱBu(BHT^*)₂	EHA	5	>99	120000	1.66	16.7
12	AlⁱBu₂(BHT^*)	EHA	5	>99	224000	1.63	8.9

硅宾/有机铝的Lewis酸碱对体系及其丙烯酸酯聚合的引发性能