Abstract
This study combined density functional theory (DFT) calculations and multivariate linear regression (MLR) to analyze the monomer poisoning effect in ethylene/polar monomer copolymerization catalyzed by the Brookhart-type catalysts. The calculation results showed that the poisoning effect of polar monomers with relatively electron-deficient functional groups is weaker, such as ethers, and halogens. On the contrary, polar monomers with electron-rich functional groups (carbonyl, carboxyl, and acyl groups) exert a stronger poisoning effect. In addition, three descriptors that significantly affect the poisoning effect have been proposed on the basis of the multiple linear regression model, viz., the chemical shift of the vinyl carbon atom and heteroatom of polar monomer as well as the metal-X distance in the σ-coordination structure. It is expected that these models could guide the development of efficient catalytic copolymerization system in this field.
Highlights
Compared with the polyolefins, the incorporation of polar monomers into nonfunctionalized polyolefin backbones can significantly improve various properties of polymers, such as flexibility, adhesion, protective properties, surface properties, solvent resistance, which leads to expanding the range of applications [1–6]
A series of complexes [11–14] have been developed on the basis of the Brookhart-type catalysts, which are only suitable for a small part of simple monomers such as acrylates [15], vinyl ketones [10], and silyl vinyl ethers [16–19]
The descriptors of heteroatom coordination structure B2 and polar monomers are calculated for multivariate linear regression
Summary
The incorporation of polar monomers into nonfunctionalized polyolefin backbones can significantly improve various properties of polymers, such as flexibility, adhesion, protective properties, surface properties, solvent resistance, which leads to expanding the range of applications [1–6]. The early-transition-metal complexes with high oxygen affinity are poisoned by polar functional groups [7] It is, necessary to use late-transition-metal complexes (Ni or Pd) with low oxygen affinity to catalyze the coordination copolymerization of polar monomers. Necessary to use late-transition-metal complexes (Ni or Pd) with low oxygen affinity to catalyze the coordination copolymerization of polar monomers In this context, various late-transition-metal catalysts have been developed (Figure 1a) [8,9]. In 2002, Drent-type catalysts were reported by Drent and co-workers (III in Figure 1a,) [20] They expanded the scope of substrate for copolymerization, such as vinyl fluoride [21], vinyl ethers [22], and some important methylene-spaced polar monomers (with a spacer between the polar group and the double bond) [23–28]. S(bev)eSreavl edriaffledreinfftepreonlatrpmoloanrommoernomer ssttrruuccttuurreess.. ((cc))ThTehecopcooplyomlyemriezraiztaiotinonmemcheacnhaisnmismof eothf yelethnyel/epneo/lparolmaronmomoneormmeerdimtaetdeidtabteydBrboyokharttByrpoeokchaatartly-tsytpseIIc.atalysts II
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