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

doi:10.6023/cjoc202305019

摘要/Abstract

研究了硅宾/有机铝组成的Lewis酸碱对(LP)体系引发丙烯酸酯类单体聚合的性能, 合成了4种硅宾: 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)、L(LSi)Si (Si-4)和6种有机铝: Al(C₆F₅)₃、AlMe(BHT)₂、AlⁱBu(BHT)₂、AlⁱBu₂(BHT)、AlⁱBu(BHT^*)₂、AlⁱBu₂(BHT^*) (BHT=2,6-^tBu₂-4-MeC₆H₂O, BHT^*=2,4,6-^tBu₃C₆H₂O). Si-1/有机铝和Si-4/有机铝LP体系均能引发甲基丙烯酸甲酯(MMA)完全聚合, 活性转换频率(TOF)值为50~400 h^-1, 产出PMMA的分子量M_n 82000~271000和分子量分布Đ 1.11~1.81. Si-2/有机铝和Si-3/有机铝LP体系没有活性. Si-1/Al(C₆F₅)₃体系对丙烯酸正丁酯(nBA)、丙烯酸-2-乙基己基酯(EHA)的活性较差, 但是Si-1/其它有机铝都能高效引发nBA和EHA完全聚合. 对nBA, TOF值4.8×10⁴~14.4×10⁴ h^-1, 产出PnBA的M_n100000~179000和Đ 1.08~1.59; 对EHA, TOF值至14.4×10⁴~36.0×10⁴ h^-1, 生成PEHA的M_n 81000~240000以及Đ 1.12~1.95. 研究了聚合反应的可能机理.

关键词: 硅宾Lewis碱, 有机铝Lewis酸, Lewis酸碱对聚合引发体系, 丙烯酸酯类单体, 聚丙烯酸酯

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

引用此文

赵怡玲, 陈志康, 李磊, 刘聪磊, 朱红平. 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[J]. 有机化学, 2023, 43(10): 3590-3597.

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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图/表 9

图1. 用于聚合的硅宾以及常见的Lewis碱的结构式

Figure 1. Schematic structures of silylenes and common Lewis bases used for polymerization

图2. 选用的4种硅宾(LB)、6种有机铝(LA)以及3种丙烯酸酯单体

Figure 2. Selected four silylenes (LB), six organoaluminums (LA), and three (meth)acrylate monomers

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

表1. 硅宾Si-1和Si-4/有机铝化合物LP体系引发MMA聚合的结果a

Table 1. MMA polymerization results by using Si-1 and Si-4/organoaluminum-based LPs

图3. Si-1/有机铝LP体系生成的PMMA样品的GPC图

Figure 3. GPC graphs of PMMA samples produced by the Si-1/ organoaluminum LP system

图4. (a) 25 ℃下Si-1/Al(C6F5)3体系产出PMMA的MALDI- TOF MS图谱([Si]由{[Si-1]-Ph＋H＋＋H?}组成的结构碎片); (b)图4(a) m/z值与MMA重复单元数(n)的关系图

Figure 4. (a) MALDI-TOF MS spectrum of the PMMA samples produced by the Si-1/Al(C6F5)3 system at 25 ℃ ([Si] is the fragment constituting of [Si-1]-Ph＋H＋＋H?); (b) plot of m/z values from Figure 4a vs the number of MMA repeated units (n)

图5. Si-2的互变异构体及其X-ray晶体结构图

Figure 5. Isomer of Si-2 and the X-ray crystal structure

图式1. 推测的[Si:]/[Al] LP体系用于MMA的聚合反应机理

Scheme 1. Proposed MMA polymerization mechanism by the [Si:]/[Al] LP system

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

表2. 硅宾Si-1/有机铝LP体系引发nBA和EHA聚合的结果a

Table 2. nBA and EHA polymerization results by using Si-1/organoaluminum LPs

图6. Si-1/有机铝 LP体系产出PEHA样品的GPC谱图

Figure 6. GPC graphs of the PEHA samples produced by the Si-1/organoaluminum LP system

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