Silicone acrylates through the hydrosilation of polyacryloyloxy functional monomers with copolymers of dimethyl and hydrogen methylsiloxanes

Abstract

James River Corporation, 191 5 Marathon Ave., Neenah, Wisconsin 54956 SYNOPSISSilicone acrylates, as possible electron beam (EB) curable release coatings for paper, were prepared by the platinum-catalyzed hydrosilation of polyacryloyloxy functional monomers with copolymers of dimethylsiloxane and hydrogen methylsiloxane (PDMHMS) . The hydrosilation of either 1,6-hexanediol diacrylate (HDDA) or trimethylolpropane triacrylate (TMPTA) with PDMHMS occurs to only one of the 2 or 3 available olefinic groups, respectively, as long as excess monomer is present. The amount of excess monomer needed to prevent gelation during hydrosilation or subsequent storage in excess of 1 month appears to be dependent on the hydrogen methylsiloxane content of the PDMHMS. A release coating having excellent cohesive and adhesive strength on paper was obtained by the EB curing of the product of hydrosilation of TMPTA with a PDMHMS containing 4 mol % hydrogen methylsiloxane at a dose-to-cure of 2 Mrad, but the aged release force was excessively high. The poor aged-release performance was likely due to dilution of the dimethylsiloxane content of the coating with excess monomer required to stabilize the silicone acrylate. 0 1993 John Wiley & Sons, Inc.

Co2(CO)8 as an efficient catalyst for the synthesis of functionalized polymethylhydrosiloxane oils and unconventional cross-linked materials

“…Additionally, the scheme depicting the cross-linked products in Table 2 illustrates that the formation of each new Si-O-Si bridge between the PMHS chains was accompanied by the formation of reduced sidechain after full reduction of the carbonyl group in the incorporated substrate. It should be noted that all the obtained gels were colored (Table 2) and in comparison to known colorless gels formed via non-precious metal catalyzed cross-linking 11,16,31 , our gels did not undergo discoloration under air in 24 h. However, while the gels were colored, they yielded slightly colored or white solids after drying at 60 °C overnight. § § Interestingly, in the case of AMA (entry 5) the product was intense blue hard glassy solid, while all the other products in Table 2 were soft gels that could easily be punctured and sliced.…”

“…For comparison, allyl (meth)acrylates have previously been incorporated into PMHS chains through the exclusive hydrosilylation of the allyl group, without evidence of cross-linking through the C=C bond in the alkenoate part of the molecule nor via ester group reduction. 31,32 This result from entry 5 suggests that, in the presence of multiple C=C and C=O bonds, the cross-linking is faster via the hydrosilylation of two C=C bonds. While unsaturated esters (entries 1-5) have demonstrated excellent aptitude as unconventional tethers, the question about the reactivity of the carbonyl group remains to be explored further.…”

Synthesis of photocrosslinkable fluorinated polydimethylsiloxanes: Direct introduction of acrylic pendant groups via hydrosilylation

“…[13][14][15][16] Up to now, the hydrosilylation synthesis of fluorinated polysiloxanes bearing acrylic groups had not been described. Thus, we were interested in studying this method to compare it to the copolycondensation method that we had previously used.…”

Hydrosilylation as an efficient tool for polymer synthesis and modification with methacrylates

“…To date, several studies on the modication of endfunctional hydride PDMS (h 2 PDMS) and copoly-(dimethyl)(methyl-hydrogen)siloxane have been reported. 19 The latter approach was used for the preparation of acrylate containing 20 and uorinated PDMS, respectively. 21 Hydrosilylation of h 2 PDMS systems was demonstrated as a technique for the introduction of (meth)acrylic acid, 22,23 amine and epoxy terminal end groups.…”

“…Synthesis of lauryl methacrylate functionalized PDMS (LMA-PDMS-LMA) 1 H NMR (CHCl 3 ): d ¼ 0.00 (m, Si-CH 3 ), 0.65 (m, Si-CH 2 ), 0.93 (m, Si-CH 2 ), 0.80 (t, CH 3 ) 1.20 (d, CH 3 ), 1.30 (m, CH 2 ) 2.5 (sex, CH), 4.00 (t, O]C-O-CH 2 ) ppm. 13 C NMR (CHCl 3 ): d ¼ 0.00 (Si-C), 9 (Si-C), 20,22,25,30,35 Synthesis of PEG 6 -b-PDMS 6 -b-PEG 6 triblock copolymer H 2 PDMS (1 g, 1.72 mmol, 1 eq.) and PEGMA (1.04 g, 3.46 mmol, 2.01 eq.)…”