High Tensile Strength UV-Cured Castor Oil-Based Silicone-Modified Polyurethane Acrylates.

High tensile strength UV-cured transparent materials are highly desired in optical devices. In this paper, high tensile strength UV-cured transparent castor oil-based polyurethane acrylates (PUAs) with a very high transmittance over 95% (400-800 nm) were prepared from UV-curable castor oil-based polyurethane acrylates (CO-PUAs) and mercapto silicone-containing hyperbranched polymers (HBPSHs) under UV irradiation. The tensile strengths of UV-cured transparent castor oil-based PUAs can reach 12.49 MPa, which is obviously higher than that of UV-cured CO-PUAs reported previously (0.7-10.20 MPa). The chemical structure of HBPSHs will play an important role in the mechanical performance of UV-cured silicone-modified materials, and it can be concluded that the more rigid the units of α,ß-dihydroxyl derivatives used in the fabrication of HBPSHs are, the higher the mechanical strength and pencil hardness of the UV-cured materials will be.

UV-Cured Transparent Silicone Materials with High Tensile Strength Prepared from Hyperbranched Silicon-Containing Polymers and Polyurethane-Acrylates.

Flexibility and mechanical performance are essential for transparent silicone materials applied in some optical and electronic devices; however, the tensile strength of transparent silicone materials is fairly low. To overcome this problem, a kind of UV-cured transparent flexible silicone material with quite a high tensile strength and elongation at break was developed through UV-initiated thiol-ene reaction by hyperbranched silicon-containing polymers (HBPs) with a thiol substitute and acrylate-terminated polyurethanes. Unexpectedly, it is found that both the tensile strength and elongation at break of the transparent silicone materials are extraordinarily high, which can reach 3.40 MPa and 270.0%, respectively. The UV-cured materials have good UV resistance ability because their transmittance is still as high as 93.4% (800 nm) even when aged for 40 min in a UV chamber of 10.6 mW cm-2. They exhibit outstanding adhesion to substrates, and the adhesion to a glass slide, wood, and a tin plate is grade 1. The promising results encourage us to further improve the mechanical performance of flexible transparent silicone materials by effective chemical modification strategies with HBPs. An attempt was made to apply the UV-cured materials in a Gel-Pak box and it could be proved that the UV-cured materials may be one of the good candidates for use as packaging or protecting materials of optical or electronics devices such as the Gel-Pak product.

High Efficiency and Low Migration Hyperbranched Silicone Contain Macrophotoinitiators for UV-Cured Transparent Coatings.

A kind of hyperbranched silicone containing macrophotoinitiators (HBSMIs) were synthesized from 2-hydroxy-2-methyl-1-phenyl propanone (HMPP) and the UV-curing behaviors of HBSMIs were investigated in UV-cured transparent polyurethane-acrylate (PUA) coatings. HBSMIs show higher UV-initiating efficiency than HMPP. The migration of HBSMIs from the UV-cured coatings can be as low as 1.7-6.0 wt%, which is obviously lower than the migration of HMPP. There is a remarkable improvement of the tensile strength of the UV-cured materials initiated by HBSMI in comparison to that of the materials prepared with the same PUA initiated by HMPP. Especially for the UV-cured materials prepared from PUA with 20 wt% 1,1,1-tris(hydroxymethyl)propane (TMP), the tensile strength and the strain at break increased from 6.81 MPa to 12.14 MPa and from 43.0% to 71.9%, respectively. The fraction of improvement for the tensile strength and the strain at break is as high as 78.9% and 67.2%, respectively. The coatings prepared with HBSMI also have better UV resistance ability than those coatings prepared with HMPP because they turn slightly yellow when they are aged by UV for about 15 min while the coating prepared with 4 wt% of HMPP will turn yellow only aged by UV for 2 min. These results suggest that preparation hyperbranched silicone containing macrophotoinitiators will be one of the good strategies to improve the curing efficiency of the UV-curing system, reduce the migration of UV initiator from cured material, improve the mechanical and UV resistance performance of UV-cured materials.

Fabrication of Transparent UV-Cured Coatings with Allyl-Terminated Hyperbranched Polycarbosilanes and Thiol Silicone Resins.

To improve thermal stability and hardness of UV-cured materials, a series of UV-cured solvent-free coatings were prepared from allyl-terminated hyperbranched polycarbosilanes and thiol silicone resins. The silicone coatings prepared have pencil hardness of 4-9 H, water absorption no more than 0.04 wt %, and transmittance higher than 94%. The temperature for the coatings' starting thermal decomposition is higher than 236 °C; especially, that of the coating prepared with G1 is as high as 371.1 °C. The UV-cured coatings in this work exhibit much higher pencil hardness than and superior thermal stability to those reported previously.

UV-Cured Transparent Flexible Silicone Materials with High Tensile Strength.

Transparent flexible silicone materials are useful in electronics, sensors, coatings, and so forth. However, to the best of our knowledge, the tensile strength of unreinforced silicone rubber is lower than 0.4 MPa, and the highest tensile strength of highly transparent silicone-modified materials is no more than 1.5 MPa. The poor mechanical property limits their further application in electronic devices. Here, a kind of UV-cured transparent flexible silicone materials with tensile strength as high as 2.2 MPa were prepared by a UV-initiated thiol-ene reaction of a sulfur-containing hyperbranched polycarbosilane and a thiol silicone resin. Interestingly, their tensile strength can increase from 2.2 to 5.6 and 5.7 MPa after being immersed in an aqueous solution of 10 wt % hydrochloric acid and 10 wt % NaCl for 7 days, respectively. It is argued that the increase of the tensile strength of cured films may be attributed to the -SiOCH3 of the residual 3-trimethoxysilylpropanethiol in the sulfur-containing hyperbranched polycarbosilane. The performances of the cured materials were investigated in detail. These silicone materials exhibit transparency higher than 95% (wavenumber in the range of 400-800 nm), and the initial thermal decomposition temperatures of the cured materials are about 340 °C. These materials also show good anticorrosion property, and the mass loss of the materials immersed in the aqueous solution mediums is no more than 0.39 wt % even for 15 days.