Synthesis and Mechanism of Metal-Mediated Polymerization of Phenolic Resins.

Zhao Yi,Shifeng Zhang,Wei Zhang,Jianzhang Li,Qiang Gao,Jizhi Zhang

doi:10.3390/polym8050159

Zhao Yi, Shifeng Zhang + Show 4 more

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https://doi.org/10.3390/polym8050159

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Journal: Polymers	Publication Date: Apr 26, 2016
Citations: 46	License type: CC BY 4.0

Affiliation: Beijing Forestry University, Shandong University

Abstract

Phenol-formaldehyde (PF) resin is a high performance adhesive, but has not been widely developed due to its slow curing rate and high curing temperature. To accelerate the curing rate and to lower the curing temperature of PF resin, four types of metal-mediated catalysts were employed in the synthesis of PF resin; namely, barium hydroxide (Ba(OH)2), sodium carbonate (Na2CO3), lithium hydroxide (LiOH), and zinc acetate ((CH3COO)2Zn). The cure-acceleration effects of these catalysts on the properties of PF resins were measured, and the chemical structures of the PF resins accelerated with the catalysts were investigated by using Fourier transform infrared (FT-IR) spectroscopy and quantitative liquid carbon-13 nuclear magnetic resonance (13C NMR). The results showed that the accelerated efficiency of these catalysts to PF resin could be ordered in the following sequence: Na2CO3 > (CH3COO)2Zn > Ba(OH)2 > LiOH. The catalysts (CH3COO)2Zn and Na2CO3 increased the reaction activity of the phenol ortho position and the condensation reaction of ortho methylol. The accelerating mechanism of (CH3COO)2Zn on PF resin is probably different from that of Na2CO3, which can be confirmed by the differences in the differential thermogravimetric (DTG) curve and thermogravimetric (TG) data. Compared to the Na2CO3-accelerated PF resin, the (CH3COO)2Zn-accelerated PF resin showed different peaks in the DTG curve and higher weight residues. In the synthesis process, the catalyst (CH3COO)2Zn may form chelating compounds (containing a metal-ligand bond), which can promote the linkage of formaldehyde to the phenolic hydroxyl ortho position.

Highlights

Phenol-formaldehyde (PF) is a high-performance resin that is synthesized by the copolymerization of phenol with formaldehyde
The catalyst-accelerated PF resin was synthesized by batch polymerization with phenol and formaldehyde at a molar ratio of 1:2.2, and the additive amount of catalyst was 6% based on the total mass of PF resin
The gel-time for the catalyst-accelerated resins varied from 11.83 min for the Na2 CO3 -accelerated resin to 20.46 min for the control resin. These results indicated that these catalysts were able to accelerate the synthesis reaction to different extents

Summary

Introduction

Phenol-formaldehyde (PF) is a high-performance resin that is synthesized by the copolymerization of phenol with formaldehyde. It is widely applied for industrial uses, including adhesives, impregnating resins, and plastics. The excellent properties of PF resin include high mechanical, thermal, and weather stability [1]. The lower curing rate and required higher curing temperature compared to other thermosetting adhesives limit the application of PF resins for use in impregnating resins or adhesives [2,3]. The effects of the condensation condition on the PF resin structure and properties have Many attempts have been made to accelerate the curing rate or lower the curing temperature, including testing of various catalysts or additives to alter the reaction kinetics, such as carboxylic acid esters [4,5], anhydrides [6], amides [7], carbonate [8], and metallic ions [9].

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