Biomaterials based on low cytotoxic vinyl esters for bone replacement application

Abstract

In recent days, additive manufacturing technologies (AMT) based on photopolymerization have also found application in tissue engineering. Although acrylates and methacrylates have excellent photoreactivity and afford photopolymers with good mechanical properties, their cytotoxicity and degradation products disqualify them from medical use. Within this work, (meth)acrylate‐based monomers were replaced by vinyl esters with exceptional low cytotoxicity. The main focus of this paper lies on the determination of the photoreactivity and investigations concerning mechanical properties and degradation behavior of the new materials. Tested monomers provide sufficient photoreactivity for processing by AMT. Mechanical properties similar to natural bone could be obtained by adding suitable fillers like hydroxylapatite (HA). The right ratio of hydrophobic and hydrophilic monomers allows the tuning of the degradation behavior. Finally, with the optimum formulation, cellular 3D structures were built using digital light processing. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.

Vinyl carbonate photopolymers with improved mechanical properties for biomedical applications

“…[29,30] However, toxicity issues [26,27] of (meth) acrylates are present also for these materials. In addition, upon degradation poly[(meth)acrylic acid] is among the degradation products, [31,32] which, in combination with the predominant autocatalytic bulk erosion mechanism of the biopolymer, [33,34] constitute large amounts of free acid of high Mw that can lead to inflammatory response and ultimately fracture due to implant failure. [35,36] Consequently, a different degradation mechanism with non-problematic degradation products together with reduced cytotoxicity and irritancy is desirable.…”

“…TTeGDMA, this value is usually well below 1 mM. [31,32,39,43] However, the dental formulation MA, which was the blueprint for the new types of vinyl carbonates and is known for its excellent for vinyl carbonates. [39] Thus, the influence of thiols onto the photoreactivity of the new vinyl carbonates was analyzed, too ( Figure 4).…”

Multiscale 3D manufacturing: combining thermal extrusion printing with additive and subtractive direct laser writing

“…[43][44][45] The potentially used material spectrum varies from biodegradable 46, 47 to hybrid 48,49 and epoxies 50,51 or vinyls. 52 It is important to mention that most of the applied materials are biocompatible in vitro 53,54 and in vivo. 55,56 In our previous report 57 we have demonstrated the possibility to combine Three-Dimensional Printing (3DP) with DLW-SM (Subtractive Manufacturing) or DLW-AM (Additive Manufacturing) approaches.…”

Preparation of divinyl esters by transvinylation between vinyl acetate and dicarboxylic acids

“…This behavior confirms the sensitivity of Pd(OAc) 2 to the temperature, due to its reduction into inactive metallic palladium, as already reported. 3 Using microwave activation, the total conversion of isophthalic acid was increased but without a real impact on divinyl isophthalate production: the monovinyl ester accumulated in the reaction medium ( 2 : no metallic palladium deposition was observed on the reactor glass. However, diacid conversion was low with no detection of divinyl ester in both cases.…”

“…Divinyl esters are also very useful in the preparation of low toxicity biomaterials by photopolymerization. 3 However, their efficient preparation remains a challenge. Only 1,10-divinyl adipate, prepared from acetylene, is commercially available, 4 while few examples of synthesis of divinyl esters are described in the literature, with generally low yields.…”