ABSTRACT
In the presented study, UV LEDs (365 nm) or a medium-pressure mercury lamp (UV-ABC) were verified as UV radiation sources initiating the photocrosslinking process of varnishes based on novel photopolymerizable phosphorus (meth)acrylate oligomers. Coating formulations were composed of (meth)acrylic/styrene telomers with terminal P-atoms (prepared via a UV phototelomerization process) and different photoinitiators (HAPs, APOs, or APO blends). The kinetics of the UV crosslinking process of the coating formulations depending on UV irradiation and the UV range was investigated by the photo-DSC method. Moreover, the hardness of the varnishes and the conversion of double bonds using the FTIR method were tested. The photopolymerization rate and the photoinitiation index, depending on the type of photoinitiator, were as follows: APOs < APO blends < HAPs. However, the highest coating hardness results were obtained using the least reactive photoinitiator from the APO group, i.e., Omnirad TPOL, or a mixture of three different types of acylphosphine (Omnirad BL 750). The greater effectiveness of the above-mentioned APOs over HAP was also demonstrated when using a UV LED lamp at 365 nm with a low UV dose and UV irradiance, thanks to the presence of phosphoric acid diester in the coating composition, acting as both a telogen and an antioxidant.
ABSTRACT
Novel pressure-sensitive adhesives (PSA) for low energy substrates were prepared by a solvent-free UV-initiated telomerization process using n-butyl acrylate, butyl methacrylate, and lauryl methacrylate (LMA), with trifluoroethanol (TFEtOH) as a telogen, and acylphosphine oxide (APO) as a radical photoinitiator. A crosslinking monomer (an aliphatic urethane acrylate, L9033) and a radical UV-photoinitiator (α-hydroxyalkylphenone) were also tested as components of the adhesive compositions. The influence of LMA and TFEtOH on the UV-phototelomerization process kinetics and the physicochemical features of the obtained fluorotelomers, as well as the concentration of L9033 on the PSA adhesion to a polyethylene surface, were investigated. FT-IR results indicated that the fluorine groups were successfully introduced into the telomer structure. The highest adhesion relative to a polyethylene substrate (12.3 N/25 mm), and the highest hydrophobicity (with a contact angle of 95° for a water/PSA system) were observed for adhesives based on a telomer syrup containing 5 wt. parts of TFEtOH and 30 wt. parts of LMA (per 100 wt. parts of the monomer mixture). Additionally, it was revealed that a higher aliphatic urethane acrylate content and a higher UV dose increased the adhesion feature.
ABSTRACT
The synthesis of novel phosphorus-containing telomers (P-telomers) was conducted via a solution-free UV-initiated telomerization process of butyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, and styrene, different phosphorus telogens (dimethyl phosphite (DMPh), dibutyl phosphite (DBPh), diphenyl phosphite (DPPh) or dibutyl phosphate (DBP)), and a radical photoinitiator-acylphosphine oxide (APO). The course of the UV-phototelomerization process was monitored by photo-DSC and the chemical structures of telomers were assessed by FTIR. Final UV-photocurable varnish compositions consisted of prepared P-telomer syrups, crosslinking monomer (pentaerythritol triacrylate; PETIA), and a radical UV-photoinitiator (α-hydroxyalkylphenone, HAP). The influence of P- telomers on the optical and mechanical features of coatings was investigated. Relatively the highest hardness and satisfactory scratch values, as well as water and solvent resistance, were observed for varnish based on DMPh-telomers. While the strongest adhesive bond to a glass substrate was reported for DPPh-telomers. It is worth pointing out that the P-telomers did not affect the gloss values of varnishes in comparison to the telomer-free reference sample.
ABSTRACT
A new method of solvent-free acrylic pressure-sensitive adhesives (PSAs) based on UV-induced cotelomerization products was presented. The key acrylic monomers (i.e., n-butyl acrylate and acrylic acid) with copolymerizable photoinitiator 4-acrylooxybenzophenone in the presence of a selected chain transfer agent (tetrabromomethane, TBM) were used in the UV-cotelomerization process. Moreover, two kinds of UV-photoinitiators (α-hydroxyalkylphenones, HPs and acylphosphine oxides, APOs) were tested. Photo-DSC, viscosity, thermogravimetric, and GPC measurements for cotelomers were performed. The kinetics study revealed that the systems with APOs, especially Omnirad 819 and Omnirad TPO, were characterized by a much higher reaction rate and greater initiation efficiency than HPs systems were. Additionally, the APO-based syrups exhibited a higher solid content (ca. 60-96 wt%), a higher dynamic viscosity (5-185 Pa·s), but slightly lower molecular weights (Mn and Mw) compared to HP syrups. However, better self-adhesive features (i.e., adhesion and tack) were observed for PSAs based on cotelomers syrups obtained using APOs with lower solid contents (55-80 wt%). It was found that as the solids content (i.e., monomers conversion) increased the adhesion, the tack and glass transition temperature decreased and the type and amount of photoinitiator had no effect on polydispersity. Most of the obtained PSAs were characterized by excellent cohesion, both at 20 °C and 70 °C.
