Tetrahydrofurfuryl acrylate: Application and Allergic contact dermatitis

Introduction

Tetrahydrofurfuryl acrylate (THFA;Figure 1) was used in various photo resins such as for the polymerization of renewable and functional latexes. Moreover, tetrahydrofuran(THF)-based photo resins were developed for the wavelength selective multi-material 3D printing as well as stereolithography printing of reprocessable acrylate vitrimers. As lignin shows a good solubility in  tetrahydrofuran and tetrahydrofurfuryl acrylat was proven to be a suitable monomer for photo-initiated 3D printing techniques, tetrahydrofurfuryl acrylat can be a promising matrix material for the digital light processing (DLP) printing of lignin composite materials.[1]

Decolorization of Lignin for High-Resolution 3D Printing of High Lignin-Content Composites

Lignin, one of the most abundant biomaterials and a large-scale industrial waste product, is a promising filler for polymers as it reduces the amount of fossil resources and is readily available. 3D printing is well-known for producing detailed polymer structures in small sizes at low waste production. Especially light-assisted 3D printing is a powerful technique for production of high-resolution structures. However, lignin acts as a very efficient absorber for UV and visible light limiting the printability of lignin composites, reducing its potential as a high-volume filler. In this work, the decolorization of lignin is presented for high-resolution 3D printing of biocomposites with lignin content up to 40 wt.%. Organosolv lignin (OSL) is decolorized by an optimized low-energy process of acetylation and subsequent UV irradiation reducing the UV absorbance by 71%. By integration of decolorized lignin into bio-based tetrahydrofurfuryl acrylate (THFA), a lignin content of 40 wt.% and a resolution of 250 µm is achieved. Due to the reinforcing properties of lignin, the stiffness and strength of the material is increased by factors of 15 and 2.3, respectively. This work paves the way for the re-use of a large amount of lignin waste for 3D printing of tough materials at high resolution.[1]

Synthesis of Thermoresponsive Shape-Memory Biobased Photopolymers 

In this work, two biobased monomers, tetrahydrofurfuryl acrylate (THFA) and tridecylmethacrylate (C13-MA), have been selected for the synthesis of photopolymers. C13-MA is derived from natural oils, and its long alkyl chains can provide flexibility for synthesized polymers. Stimuli-responsive materials are known as smart materials because they are aware of environmental stimuli and can give straight responses. Many biobased polymers with great shape-memory properties were obtained. A series of thermoresponsive shape-memory photopolymers have been synthesized from the mixtures of two biobased monomers, tetrahydrofurfuryl acrylate and tridecyl methacrylate, with the addition of a small amount of 1,3-benzendithiol (molar ratio of monomers 0-10:0.5:0.03, respectively). Ethyl (2,4,6 trimethylbenzoyl) phenylphosphinate was used as photoinitiator. The calculated biorenewable carbon content of these photopolymers was in the range of (63.7-74.9)%. The increase in tetrahydrofurfuryl acrylate content in the photocurable resins resulted in a higher rate of photocuring, increased rigidity, as well as mechanical and thermal characteristics of the obtained polymers. All photopolymer samples showed thermoresponsive shape-memory behavior when reaching their glass transition temperature. The developed biobased photopolymers can replace petroleum-derived thermoresponsive shape-memory polymer analogues in a wide range of applications.[2]

Allergic contact dermatitis caused by tetrahydrofurfuryl acrylate

Report 1

Tetrahydrofurfuryl acrylate (THFA) and tetrahydrofurfuryl methacrylate (THFMA) are components of acrylic adhesives. Although a positive reaction to THFMA has been considered a cross-reaction to other acrylic resins, Moffitt et al reported patients sensitized by tetrahydrofurfuryl acrylate.A 44-year-old woman with no history of contact or atopic dermatitis had purchased clip-on earrings approximately 5 months ago and wore them several times without symptoms. One day, after wearing the earrings for several hours, she noticed erythema on her earlobes where they were in contact with the resin of the earrings. Her symptoms improved withtopical steroids.The patient was sensitized to tetrahydrofurfuryl acrylate from wearing the causative clip-on earrings. As she showed a positive reaction only to THFA and THFMA, doctors assumed that other acrylic resins had no cross-reactions in case of sensitization with tetrahydrofurfuryl acrylate.THFMA and THFA are used in printing ink, ultraviolet light-curable adhesive coatings, and paint because of the low viscosity and adhesion. Contact dermatitis due to tetrahydrofurfuryl acrylate used in everyday products may increase in the future.[3]

Report 2

A 34-year-old atopic woman gave a history of a blistering rash on the lateral borders of the fingers on both hands, and itching with redness and dryness of her nose and eyelids. She worked as a machine operator for a company assembling surgical needles. A new medical device adhesive had been introduced 2 months prior to the onset of the rash. She had been exposed to the product both accidentally and when filling a machine and had not been adequately protected. She was removed from her working environment and the rash settled within a week. Examination at the time of patch testing was normal.Patch testing was performed using Finn Chambers.She was patch tested to the British standard series and preservative, facial, plastics and glues, and isocyanate series. Patch testing to the adhesive 0.1% and 1% pet.and its components was performed. She had a positive(+) reaction at 2 and 4 days (D) to tetrahydrofurfuryl acrylate 0.2% and 2% pet. Acrylic resins have a wide range of uses, including plastics, adhesives, paints, inks and coatings in the printing industry, bone cement and denture manufacturing.Tetrahydrofurfuryl acrylate is a polyfunctional acrylate.Polyfunctional acrylates (which have at least 2 reactive acrylic groups) are particularly used in printing inks and dental adhesives.[4]

References

[1] Böcherer D, Montazeri R, Li Y, Tisato S, Hambitzer L, Helmer D. Decolorization of Lignin for High-Resolution 3D Printing of High Lignin-Content Composites. Adv Sci (Weinh). 2024;11(39):e2406311. doi:10.1002/advs.202406311

[2] Jaras J, Navaruckiene A, Ostrauskaite J. Thermoresponsive Shape-Memory Biobased Photopolymers of Tetrahydrofurfuryl Acrylate and Tridecyl Methacrylate. Materials (Basel). 2023;16(6):2156. Published 2023 Mar 7. doi:10.3390/ma16062156

[3] Suzuki K, Matsunaga K, Sasaki K, Yagami A. Allergic contact dermatitis caused by tetrahydrofurfuryl acrylate in the adhesive of clip-on earrings. Contact Dermatitis. 2020;82(2):131-133. doi:10.1111/cod.13412

[4] Moffitt DL, Sansom JE. Occupational allergic contact dermatitis from tetrahydrofurfuryl acrylate in a medical-device adhesive. Contact Dermatitis. 2001;45(1):54. doi:10.1034/j.1600-0536.2001.045001054.x

You may like