Accelerating Research into Bio-Based FDCA-Polyesters by Using Small Scale Parallel Film Reactors

Abstract

High Throughput experimentation has been well established as a tool in early stage catalyst development and catalyst and process scale-up today. One of the more challenging areas of catalytic research is polymer catalysis. The main difference with most non-polymer catalytic conversions is the fact that the product is not a well defined molecule and the catalytic performance cannot be easily expressed only in terms of catalyst activity and selectivity. In polymerization reactions, polymer chains are formed that can have various lengths (resulting in a molecular weight distribution rather than a defined molecular weight), that can have different compositions (when random or block co-polymers are produced), that can have cross-linking (often significantly affecting physical properties), that can have different endgroups (often affecting subsequent processing steps) and several other variations. In addition, for polyolefins, mass and heat transfer, oxygen and moisture sensitivity, stereoregularity and many other intrinsic features make relevant high throughput screening in this field an incredible challenge. For polycondensation reactions performed in the melt often the viscosity becomes already high at modest molecular weights, which greatly influences mass transfer of the condensation product (often water or methanol). When reactions become mass transfer limited, catalyst performance comparison is often no longer relevant. This however does not mean that relevant experiments for these application areas cannot be performed on small scale. Relevant catalyst screening experiments for polycondensation reactions can be performed in very efficient small scale parallel equipment. Both transesterification and polycondensation as well as post condensation through solid-stating in parallel equipment have been developed. Next to polymer synthesis, polymer characterization also needs to be accelerated without making concessions to quality in order to draw relevant conclusions.

Biobased polyesters and other polymers from 2,5-furandicarboxylic acid: a tribute to furan excellency

“…11,12,14,25,30,31,40,110 In 2012 Gruter et al 109 published an in-depth systematic study about several parameters affecting this 2-(or 3-) stage polymerisation approach, namely starting monomers, temperature, and especially the catalysts used. These parameters were assessed in terms of colour, yields and molecular weight.…”

“…In the same vein, increasing the polymerisation temperature up to 260-280 o C, as used in PET counterpart, resulted in yellowish coloured products (a really huge problem in certain applications like for example in packaging) and lower yields. An extensive catalyst screening was carried out in this same study, 109 in which 45 different metal catalysts were compared. Results revealed that the highest yields were obtained for dibutyltin(IV) oxide and titanium(IV) isopropoxide, although when the former was used a more coloured product was obtained.…”

A facile method to synthesize high‐molecular‐weight biobased polyesters from 2,5‐furandicarboxylic acid and long‐chain diols

“…Such times are too high and can cause coloration to the final polyester. With the method proposed in the current study, the coloration is limited, as was mentioned in previous studies, and is temperature dependent …”

“…The coloration of the FDCA/2,5‐dimethylfuran dicarboxylate (DMFD)‐based materials can have three origins, namely, sugar‐based impurities in the monomer, side reactions (e.g., decarboxylation) taking place during the polymer synthesis, or the presence of various additives . It was also found that catalysts such as manganese, cobalt, and germanium result in a strongly colored PEF product . Furthermore, as was reported by de Jong et al, there is a clear relationship between the amount of FDCA and the amount of color formed.…”

Monomers and Resulting Polymers from Biomass

“…A specific target is poly(ethylene terephthalate) (PET), which is a fossil-based polyester with a market volume of 50 million tons per year [93]. Several groups have investigated furan analogs to PET using the 2,5-FDCA furan derivative [89,91,92,[94][95][96][97]. There are several synthetic routes to polyesters based on FDCA, including solution polycondensation, polytransesterification, and solid-state postcondensation [91,92].…”