European Conference on Smart & Functional Coatings September 2013, Torino, Italy

SILOXANEBASEDUVCUREDCOATINGS

A.Vitale1,S.Turri2,R.Bongiovanni1

DISAT,PolitecnicodiTorino,c.DucadegliAbruzzi24,10129Torino,Italy 2 CMIC,PolitecnicodiMilano,P.zzaL.daVinci32,20133Milano,Italy

Abstract An optically transparent coating is obtained by UVcuring a difunctional acrylate containing alinearchainmadeofasiloxaneblockandapolyoxyethyleneblock.Themacromerishighly photoreactive and by irradiation gives a transparent rubbery polymer, resistant to temperature. The high crosslinking degree enhances the solvent resistance and assures dimensionalstability.Thefilmisbiocompatible,hydrophobicandoleophobic. Introduction There is a high interest in reactive silicone fluids for UVcurable coatings due to their peculiar properties such as softness, good thermal stability, substrate wettability, etc[1]. The applications of these coatings can span from optics/photonics, to release/antisticking coatings and transparent antisoiling coatings. The main disadvantage is that silicones are nonpolar and nonmiscible with the photoinitiator and other resins. This work discusses the polymerisation of a difunctional acrylate containing a chain made of a siloxane block and a polyoxyethylene block, able to cure under UV light, in the presence of common photoinitiators;thepropertiesofthecuredfilmareinvestigated. Experimental ThephotocurablemacromerisCoatOSil3503(Mn=1900,MomentiveLtd): The photoinitiator is 2hydroxy2methyl1phenylpropan1one (Aldrich, 3% wt). The reactive formulation is spin coated on Si wafers and then cured under N2. The curing conversionismonitoredbyFTIR,DSC,gelcontent(byCHCl3extraction).Characterisationof thecoatingsismadebyDSC,TGA,DMTA,wettability,swellingandbiocompatibilitytests. ResultsandDiscussion The spin coating technique was adopted to coat Si wafer substrates with the silicone acrylatemacromer:thespinningcurveisinFigure1.Thekineticsofphotopolymerizationof 7mthickfilm(Hglamp,I=3mWcm2atthefilmsurface)wasmonitoredbythreedifferent techniques(Figure2,left):theresultsareingoodagreementandamaximumconversionof about80%isobtainedin35s.

European Conference on Smart & Functional Coatings September 2013, Torino, Italy

20

Film thickness (m)

15 10 5 0 0 1000 2000 3000 4000

Spinning speed (rpm)

Figure1.Spinningcurveofthesiloxaneacrylate.

The GT behaviour of the coatings (Figure 2 right) is typical of an efficiently crosslinked amorphous polymer, with a sharp decrease in modulus at the phase transition. The crosslinkingdensityoftheUVcuredfilm,asestimatedfromGattherubberyplateau,is= 0.256mmolcm3,theTg=37.6Catf=1HzinagreementwiththeDSCmeasurements.

Figure2.Left:Conversion%curvesbyFTIR,DSCandinsolublefractionmeasurement. Right: StoragemodulusGatvarioustemperaturesandfrequenciesofthesiliconeacrylatecrosslinkedpolymer

The coatingobtained is thermal resistant: inairit does not degrade till 199C (T5), while the 50% weight loss is recorded at 365C (T50).The film is pretty hydrophobic with a contact angle against water around 94. Its surface tension is 21 mN/m. In agreement with these results,thematerialhasagoodstabilityinwater:after24hourstheswellingis16%. In vitro DNA amplification tests were carried out in the presence of the siloxane acrylate film:thematerialdidnotinhibitedthereaction.

Conclusions By a radical photoinduced polymerization we obtained a highly crosslinked coating characterised by interesting properties: thermal stability, water inertness, dimensional stability, optical transparency. Due to the acrylic end groups, the photoreactivity was high; as the macromer contained a siloxane backbone with ethoxy groups, the final UVcured polymerwashydrophobicanddidnotinhibitedDNAreplicationreactions. References [1] J.P.Fouassier,X.Allonas,J.Laleve,C.Dietlin,in:Photochemistryandphotophysicsof polymermaterials,N.S.Alleneditor(WileyVCH,Weinheim,2010),p.351419.