Evaluation of Difunctional Vinylcyclopropanes as Reactive Diluents for the Development of Low‐Shrinkage Composites

Polymerization shrinkage of dental composites remains a major concern. Free‐radically polymerizable cyclic monomers can be a conceivable alternative to methacrylates for the development of low‐shrinkage composites. In this study, the one‐step synthesis of the novel low viscosity difunctional vinylcyclopropanes 1 – 4 is described. Photopolymerization kinetics of these monomers are investigated by photo‐differential scanning calorimeter, using bis(4‐methoxybenzoyl)diethylgermane as photoinitiator. Real‐time near‐infrared photorheology measurements are performed to evaluate rheological behavior (i.e., time of gelation, polymerization‐induced shrinkage force) and chemical conversion (i.e., double bond conversion at the gel point, final double bond conversion) of the vinylcyclopropanes in situ. The potential of these monomers as reactive diluents in dental restorative materials is evaluated. Composites based on vinycyclopropanes 1 – 4 show good mechanical properties and exhibit significantly lower volumetric shrinkage and shrinkage stress than corresponding dimethacrylate‐based materials. The results indicate that such monomers are promising candidates for the replacement of commonly used low viscosity dimethacrylates such as triethylene glycol dimethacrylate in dental composites.

     

Polymerization of cyclic monomers. VII. Synthesis and radical polymerization of 1,3‐bis[(1‐alkoxycarbonyl‐2‐vinylcyclopropane‐1‐yl)carboxy]benzenes

1,3‐Bis[(1‐alkoxycarbonyl‐2‐vinylcyclopropane‐1‐yl)carboxy]benzenes 1 [RO: CH₃O (a), C₂H₅O (b)] were synthesized by the esterification of the corresponding 1‐alkoxycarbonyl‐2‐vinylcyclopropane‐1‐carboxylic acids with resorcinol. The structure of the new vinylcyclopropanes was confirmed by elemental analysis and infrared (IR), ¹H nuclear magnetic resonance (¹H‐NMR), and ¹³C nuclear magnetic resonance (¹³C‐NMR) spectroscopy. The radical polymerization of difunctional 2‐vinyl‐cyclopropanes in bulk with 2,2′‐azoisobutyronitrile (AIBN) results in hard, transparent, crosslinked polymers. During the bulk polymerization of the crystalline bis[(1‐methoxycarbonyl‐2‐vinylcyclopropane‐1‐yl)carboxy]benzene 1a, an expansion in volume of about 1% took place. The radical solution polymerization of 1a resulted in a soluble polymer with pendant 2‐vinylcyclopropane groups. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1775–1782, 1999     

Synthesis of acidic vinylcyclopropanes for dental applications

The multistep synthesis of four new acidic vinylcyclopropanes is described. These monomers were fully characterized using ¹H NMR, ¹³C NMR and ³¹P NMR spectroscopy and high‐resolution mass spectrometry. The homopolymerization of the corresponding polymerizable di‐tert‐butyl phosphates as well as the copolymerization of each acidic monomer with 1,1‐diethoxycarbonyl‐2‐vinylcyclopropane were investigated using photo‐differential scanning calorimetry with bis(4‐methoxybenzoyl)diethylgermane as photoinitiator. Self‐etch adhesives based on the synthesized acidic vinylcyclopropanes are able to achieve a strong bond between a dental composite and both dentin and enamel. Flowable composites containing these acidic vinylcyclopropanes exhibit good mechanical properties. The replacement of methacrylates by vinylcyclopropanes leads to a significant reduction of the shrinkage stress of flowable composites. © 2017 Society of Chemical Industry     

Polymerization of ϵ‐caprolactone initiated through powders of biological and nonbiological glasses

Eight biomedical glasses and three commercial glasses, as finely divided powders, were tested as initiators for the ring‐opening polymerization of ?‐caprolactone in bulk and in vacuo at 185°C. All the glass powders were able to initiate the polymerization, along with Pyrex, which was totally inert toward the monomer as the inner surface of a phial. The obtained polymers were examined with Fourier infrared transform spectroscopy and atomic force microscopy. The molecular weights were measured by viscometry in CHCl₃. The presence of a fraction of the polymer firmly linked to the glass was quantitatively checked by the determination of the weight loss from the residues of the extraction with CHCl₃ after calcination in a kiln at 945°C. The molecular weights and weight losses per unit surface were elaborated mathematically so that a possible correlation between these properties and the atomic compositions of the glasses could be better investigated. Two possible initiation mechanisms, induced by the hydroxyls present on the glass surface, were proposed: one for free poly(?‐caprolactone) and one for poly(?‐caprolactone) linked to the glass. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1579–1586, 2003     

Monomers for Adhesive Polymers, 4

Hydrolytically stable, crosslinking bis(acrylamide)s 1a – 1l or bis(methacrylamide)s 2a – 2c were synthesized by reaction of acryloyl or methacryloyl chloride using primary or secondary amines. In addition, monomers 3a and 3b were obtained by amidation of 2,6‐dimethylene‐4‐oxaheptane‐1,7‐dicarboxylic acid (DMOHDA) with propylamine and diethylamine, respectively. The structures of the monomers were characterized by IR, ¹H, and ¹³C NMR spectroscopy. All monomers containing N,N′‐monosubstituted carbamide groups were solids. Those containing N,N′‐disubstituted carbamide groups were water‐soluble liquids. Water‐soluble bis(acrylamide) 1d (N,N′‐diethyl‐1,3‐bis(acrylamido)propane) shows a radical polymerization reactivity in the presence of 2,2′‐azobis(2‐methylpropionamidine) dihydrochloride (AMPAHC) similar to that of glycerol dimethacrylate, as revealed by gelation experiments in water. 1d is hydrolytically stable in 20 wt.‐% phosphoric acid and can be used to substitute dimethacrylates in self‐etching dentin adhesives. Furthermore, this monomer was also suitable as a reactive diluent in composites.

     

Photopolymerization of a novel tetraoxaspiroundecane and silicon‐containing oxiranes

New multifunctional silorane‐based systems were investigated, with respect to their photoreactivity, as potential matrix resins for low‐shrinkage/stress dental composites. The objective of this investigation was to synthesize and evaluate the reactivity of a silicon‐analogue oxaspirocyclic monomer with silorane‐based matrix resin systems during visible‐light polymerization. The experimental formulations contained (1) a silicon‐containing 1,5,7,11‐tetraoxaspiro[5.5]undecane (TOSU– IV ), (2) a phenylmethylsilane containing two cyclohexyloxiranyl groups, (3) a cyclotetrasiloxane containing four cyclohexyloxiranyl groups, and (4) a photocationic initiator system. Three main aspects were studied: (1) the photoreactivity of the tetraoxaspiroundecane (TOSU)/silorane reactant mixtures with differential scanning photocalorimetry, (2) oxirane ring‐opening reactions of siloranes during binary photopolymerization with Fourier transform infrared (FTIR), and (3) oxaspirocyclic ring‐opening reactions of the TOSU reactant during homophotopolymerization and binary photopolymerization with FTIR and NMR. A diallyl ether precursor of TOSU– IV was also included in selected studies. The main findings were as follows: (1) a feasible route for the successful synthesis of a silicon analogue (TOSU– IV ) was developed; (2) TOSU– IV was compatible and photoreactive, making possible the reduction of polymerization stress in silorane‐based matrix resins; and (3) spectroscopic evidence for both oxirane and oxaspirocyclic ring opening during the visible‐light photopolymerization of the test formulations was found. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 336–344, 2007     

Monomers for Adhesive Polymers, 9–Synthesis,Radical Photopolymerization,and Properties of (Meth)acrylamido Dihydrogen Phosphates

5‐Methacrylamidopentyl ( 3a ), 10‐(N‐methylacrylamido)decyl ( 3b ), or 11‐(N‐methylacrylamido)undecyl dihydrogen phosphate ( 3c ) are synthesized by (meth)acrylation of the corresponding ω‐aminoalkane‐1‐ols with methacrylic anhydrid or acryloyl chloride followed by phosphorylation of the formed ω‐(meth)acrylamidoalkane‐1‐ols. The monomers show a significantly improved hydrolytic stability compared to the corresponding methacrylate‐based dihydrogen phosphates. The photopolymerization of 3a–c with a bis(acrylamide) crosslinker confirms a high reactivity in the free‐radical copolymerization. These monomers enable the mediation of a strong bond between the enamel or dentin surface and a restorative composite under self‐etching conditions.

     

Recent Developments of New Components for Dental Adhesives and Composites

The currently used commercial self‐etching enamel‐dentin adhesives and restoratives composites are mainly based on a mixture of various monofunctional and cross‐linking dimethacrylates. New developments of enamel‐dentin adhesives concern the improvement of technique insensitivity and storage stability. Improvements of restorative composites are focused on the reduction of the polymerisation shrinkage, as well as the improvement of wear resistance, biocompatibility, and processing properties. In the past five years, many research efforts have been carried out to develop new monomers and tailor‐made components for filling materials, such as fillers or initiators. New phosphonic acid ether acrylates and cross‐linking bis(acrylamide)s enable the preparation of self‐etching enamel‐dentin adhesives with improved storage stability. With free‐radically polymerisable cyclic monomers, such as bicyclic cyclopropyl acrylates or cyclic allyl sulfides, low‐shrinkage storage‐stable restorative composites could be prepared. In case of the cationic polymerisable cyclic monomers, like siloxane‐based cycloaliphatic epoxides, the lower curing rate, stronger exothermic effect and lower curing depth compared to dimethacrylate‐based composites presently prevent their dental application. Designed methacrylates with tailor‐made properties and sol‐gel polycondensates can also contribute to the improvement of the currently used restorative composites. Radical polymerisable dental materials are initiated by light curing and by redox initiator systems. Under acidic conditions amine containing initiator systems are deactivated by acid‐base reaction. Non amine‐based initiators have to be developed for acidic monomer containing dental materials. The use of discrete nano‐filler particles mainly concerns the reinforcement and, in some cases, the increase of X‐ray opacity of composite filling materials.

     

Block and Random Living,Ring‐Opening Metathesis Copolymerization of Functionally Differentiated Carbazole‐Containing Norbornene Monomers

The synthesis of novel diblock polymers containing both a potential charge transport and a non‐linear optic block has been accomplished. The synthesis exploits the living, ring‐opening metathesis block copolymerization of two norbornene type monomers, one of which contains an unsubstituted N‐carbazolyl ring while the other has a bromo substituent at the 3‐position of the carbazole ring. Conversion of the bromo functionality to a 2,2‐dicyanovinyl group introduces the non‐linear optic property. The first monomer was prepared by the previously reported efficient cation radical Diels–Alder cycloaddition of N‐trans‐1‐propenylcarbazole to 1,3‐cyclopentadiene, while the second was obtained by N‐bromosuccinimide bromination of the first monomer. For purposes of comparison, the corresponding random copolymer was also synthesized.     

An Efficient Synthesis of Ring‐Opening Metathesis Monomers and Polymers Containing Carbazole and Other Electron‐Rich Moieties

An efficient synthesis of ring‐opening metathesis monomers and polymers containing ionizable moieties such as N‐carbazolyl, 2‐dibenzofuranyl, 2‐dibenzothiophenyl, and 4‐anisyl functionalities has been developed, using cation radical Diels‐Alder cycloaddition chemistry to generate the appropriate norbornene‐type monomers.     

Tetrahydrosalen‐stabilized,chloride‐containing rare‐earth complexes: Facile initiator precursors for the preparation of hydroxytelechelic poly(ε‐caprolactone)s

End‐capped poly(ε‐caprolactone)s (PCLs) have been prepared elsewhere by various initiators. However, hydroxytelechelic PCLs have been reported less frequently, although there are two hydroxyl end groups in one polymer chain, which allows diversified functionalization. Two tetrahydrosalen‐backboned chlorides containing rare‐earth complexes, YbLCl(DME)₂ and ErLCl(DME) {where L is 6,6′‐[ethane‐1,2‐diylbis(methylazanediyl)]bis (methylene)bis(2,4‐di‐tert‐butylphenol) and DME is dimethoxyethane}, were first synthesized in this study, and they were used as initiator precursors for a ring‐opening polymerization in the presence of NaBH₄ to afford hydroxytelechelic PCLs. The polymerization under different conditions was investigated, and a possible mechanism is proposed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

New polymer materials based on silicone‐acrylic copolymer to improve fastness properties of reactive dyes on cotton fabrics

New polymer materials, based on silicone‐acrylic copolymer containing cationic groups, were synthesized through radical mechanism and ring‐opening polymerization of cyclosiloxane. The polymers of polyacrylate/polysiloxane improved the fastness properties of reactive dyes on cotton. In comparison with those of polyacrylate‐containing cationic groups, the wash fastness and wet rubbing fastness of the dyed cotton fabric treated with the new polymer materials were better. The handle of the fabric with aftertreatment was also good. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 720–725, 2006     

A new macroinitiator for the synthesis of triblock copolymers PA12‐b‐PDMS‐b‐PA12

A new PDMS macroinitiator is proposed for the anionic ring‐opening polymerization of lactams. This α,ω‐dicarbamoyloxy caprolactam PDMS macroinitiator was readily obtained in quantitative yield, by an original synthesis scheme in two steps, which involved the scarcely reported reaction of isocyanates with silanol groups. It was then shown that this bifunctional macroinitiator enabled to synthesize triblock copolymers PA12‐b‐PDMS‐b‐PA12 by polymerization of lauryl lactam (LL) at high temperature (200°C) in inert atmosphere under conditions compatible with reactive extrusion processes. Another related high molar weight α,ω‐diacyllactam PDMS macroinitiator was also successfully used in the polymerization of LL under the same conditions, therefore overcoming the limitations formerly reported for this type of macroinitiators during the polymerization ε‐caprolactam (ε‐CL) at a much lower temperature (80°C). Triblock copolymers with a wide range of PA12 /molar weights (M_n: ～ 10,800–250,000 Da) were eventually obtained by using both types of macroinitiators. DMTA and DSC analyses showed that their thermal properties were strongly dependent upon their respective contents in soft and hard blocks. Such triblock copolymers already appear very promising for the highly effective in situ compatibilization of PA12/PDMS blends as shown by recent complementary results obtained in our laboratory. © 2006 Wiley Periodicals, Inc. J Appl PolymSci 102: 2818–2831, 2006     

Easily Accessible Ring Opening Metathesis and Atom Transfer Radical Polymerization Catalysts based on Arene,Norbornadiene and Cyclooctadiene Ruthenium Complexes Bearing Schiff Base Ligands

A group of four mixed ligand ruthenium(II)‐Schiff base complexes has been synthesized and characterized. These complexes are easily accessible from [RuCl₂(p‐cymene)]₂, [RuCl₂(NBD)]_n, [RuCl₂(COD)]_x and salicylaldimine salts. They have been found to serve as good catalyst precursors for ring‐opening metathesis polymerization (ROMP) and atom transfer radical polymerization (ATRP) of different vinyl monomers. The catalytic activity and the control over the produced polymer can be dramatically improved after the addition of additives such as Et₂AlCl and (n‐Bu)₂NH.     

Polymerization of 3‐glycidyloxypropyltrimethoxysilane with different catalysts

Polymerization reactions of 3‐glycidyloxypropyltrimethoxysilane (GPTS) were carried out by different catalysts, potassium hydroxide, potassium tert‐butoxide, and tetraphenylporphyrin aluminum chloride (TPP–AlCl), and tetrafluorophthalate zironium isopropoxide complex. Polymer samples obtained from the ring‐opening polymerization of GPTS were characterized by Fourier transform infrared spectroscopy, NMR spectroscopy, electrospray ionization mass spectroscopy, and gel permeation chromatography. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Magnetic Characteristics of Ferrimagnetic Microspheres Prepared by Dispersion Polymerization

Summary: A magnetite‐based colloid was obtained by chemical co‐precipitation of iron(II) and iron(III) salts in alkaline medium and stabilized with oleic acid. Magnetic micron‐size poly(2‐hydroxyethyl methacrylate) (PHEMA)‐based latex particles of narrow size distribution were prepared by dispersion polymerization in toluene/2‐methylpropan‐1‐ol in the presence of three kinds of ferrimagnetic nanoparticles: chromium dioxide, maghemite, and magnetite. Cellulose acetate butyrate and dibenzoyl peroxide were used as the stabilizer and the initiator, respectively. The magnetic characteristics were examined with respect to behavior in the magnetic field and thermal stability. Our results show that chromium dioxide and derived PHEMA particles are magnetically stable in moderate temperatures up to about 100 °C. Maghemite particles are thermally stable up to 500 °C. Measurements of the hysteresis loops and remanent magnetization showed that embedment of magnetic particles in organic polymer has practically no effect on their magnetic hysteresis. All the samples reached magnetic saturation in fields below 0.3 T (saturation of magnetite). Regarding separation by the magnetic field, ultrafine, superparamagnetic magnetite particles show the best performance because of their magnetic susceptibility, the highest measured here, and the absence of coercive force.

Scanning electron micrograph of magnetite‐containing P(HEMA‐co‐25% GMA) microspheres.     

Reactions of trithiocyanuric acid with oxiranes. IV. Analysis of the initial stages of the synthesis of polyetherols

The course of the reaction of trithiocyanuric acid (TTCA) with oxiranes, propylene oxide (PO), and epichlorohydrin in a dimethyl sulfoxide solution was monitored by the acid number and epoxy number. The involvement of one of the tautomers of TTCA was postulated on the basis of the studied reaction between TTCA and 3 equiv of oxirane. It was also evidenced that the use of a catalyst was necessary for the reaction between TTCA and an excess of PO. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4917–4920, 2006     

Gold(I)‐ and Brønsted Acid‐Catalyzed Ring‐Opening of Unactivated Vinylcyclopropanes with Sulfonamides

The gold(I)‐ or Brønsted acid‐catalyzed reaction of unactivated vinylcyclopropanes (VCPs) with sulfonamides affords useful homoallylic amine derivatives. This ring‐opening reaction occurs in a highly selective manner affording in the case of α‐phenyl‐substituted VCPs products with the E‐configuration exclusively.     

Bio‐Based Rubbers by Concurrent Cationic and Ring‐Opening Metathesis Polymerization of a Modified Linseed Oil

Bio‐based rubbers prepared by tandem cationic polymerization and ROMP using a norbornenyl‐modified linseed oil, Dilulin?, and a norbornene diester, NBDC, have been prepared and characterized. Increasing the concentration of the NBDC in the mixture results in a decrease in the glass transition temperature. The new bio‐based rubbers exhibit tensile test behavior ranging from relatively brittle (18% elongation) to moderately flexible (52% elongation) and with decreasing values of tensile stress with increasing NBDC content. Thermogravimetric analysis reveals that the bio‐based rubbers have maximum decomposition temperatures of over 450 °C with their thermal stability decreasing with increasing loadings of NBDC.