Polymerization Of Methacrylate Monomers Research Articles

SYNTHESIS OF COPOLYMERS OF STEARYLMETHACRYLATE AND STEARYLACRYLATE WITH N-SUBSTITUTED ACRYLAMIDES IN THE PRESENCE OF REVERSIBLE CHAIN TRANSFER AGENTS AND STUDY OF THEIR EFFECT ON THE LOW-TEMPERATURE PROPERTIES OF DIESEL FUEL

The features of copolymerization of stearylacrylate (SA) and stearylmethacrylate with N-isopropylacrylamide and N,N-dimethylacrylamide in the presence of dibenzyltrithiocarbonate and 2-cyanoisopropyldodecyltrithiocarbonate as agents of reversible chain transfer have been studied. The choice of agents of reversible chain transfer (RAFT-agents) is due to the fact that sulfur-containing compounds with cyanoisopropyl radicals are most effective in the polymerization of methacrylic monomers, while benzyltrithiocarbonates are more active in the polymerization of acrylic monomers, as well as styrene and acrylonitrile. It has been established that polymerization of stearyl methacrylate (SMA) in the presence of RAFT-agents proceeds without a gel effect up to a high conversion. At the same time, although polystеarylmethacrylate samples are characterized by relatively high values of polydispersity coefficients (Mn/Mw) for controlled radical polymerization processes, they are nevertheless somewhat lower than for polymers of similar conversion synthesized in the absence of chain transfer agents. It has been shown that the process of copolymerization of stearyl acrylate and stearylmethacrylate with N-isopropylacrylamide and N,N-dimethylacrylamide in the presence of dibenzyltrithiocarbonate and 2-cyanoisopropyldodecyltrithiocarbonate proceeds without gelation to high conversions. The synthesized copolymers are characterized by a relatively narrow molecular weight distribution: the polydispersity coefficients of polymer samples vary from 1.18 to 1.57 in the case of using N-isopropylacrylamide and from 1.21 to 1.47 when using N,N-dimethylacrylamide as a comonomer to higher alkyl acrylates, which is typical for processes of radical polymerization proceeding in a controlled manner. At the same time, the synthesized copolymers exhibit a significant depressant effect when they are introduced into diesel fuel at a concentration of 1600 ppm. It has been established that copolymers of stearylmethacrylate and stearylacrylate with polar nitrogen-containing monomers have a more effective effect on the low-temperature properties of diesel fuel than homopolymers of stearylmethacrylate and stearylacrylate. At the same time, additives based on copolymers of stearylmethacrylate with N-isopropylacrylamide with a composition of 70/30 mol.% and stearylacrylate with N-isopropylacrylamide with a composition of 20/80 mol.% had the most significant effect on the low-temperature characteristics of the fuel.

The Role of Polymer Structure in Formation of Various Nano- and Microstructural Materials: 30 Years of Research in the Laboratory of Nano- and Microstructural Materials at the Centre of Polymer and Carbon Materials PAS.

The review summarizes the research carried out in the Laboratory of Nano- and Microstructural Materials at the Centre of Polymer and Carbon Materials, Polish Academy of Sciences (CMPW PAS). Studies carried out for many years under the guidance of Professor Andrzej Dworak led to the development and exploration of the mechanisms of oxirane and cyclic imine polymerization and controlled radical polymerization of methacrylate monomers. Based on that knowledge, within the last three decades, macromolecules with the desired composition, molar mass and topology were obtained and investigated. The ability to control the structure of the synthesized polymers turned out to be important, as it provided a way to tailor the physiochemical properties of the materials to their specific uses. Many linear polymers and copolymers as well as macromolecules with branched, star, dendritic and hyperbranched architectures were synthesized. Thanks to the applied controlled polymerization techniques, it was possible to obtain hydrophilic, hydrophobic, amphiphilic and stimulus-sensitive polymers. These tailor-made polymers with controlled properties were used for the construction of various types of materials, primarily on the micro- and nanoscales, with a wide range of possible applications, mainly in biomedicine. The diverse topology of polymers, and thus their properties, made it possible to obtain various types of polymeric nanostructures and use them as nanocarriers by encapsulation of biologically active substances. Additionally, polymer layers were obtained with features useful in medicine, particularly regenerative medicine and tissue engineering.

Controlled (Co)Polymerization of Methacrylates Using a Novel Symmetrical Trithiocarbonate RAFT Agent Bearing Diphenylmethyl Groups.

Herein, we report a novel type of symmetrical trithiocarbonate chain transfer agent (CTA) based diphenylmethyl as R groups. The utilization of this CTA in the Reversible Addition-Fragmentation chain Transfer (RAFT) process reveals an efficient control in the polymerization of methacrylic monomers and the preparation of block copolymers. The latter are obtained by the (co)polymerization of styrene or butyl acrylate using a functionalized macro-CTA polymethyl methacrylate (PMMA) previously synthesized. Data show low molecular weight dispersity values (Đ < 1.5) particularly in the polymerization of methacrylic monomers. Considering a typical RAFT mechanism, the leaving groups (R) from the fragmentation of CTA should be able to re-initiate the polymerization (formation of growth chains) allowing an efficient control of the process. Nevertheless, in the case of the polymerization of MMA in the presence of this symmetrical CTA, the polymerization process displays an atypical behavior that requires high [initiator]/[CTA] molar ratios for accessing predictable molecular weights without affecting the Đ. Some evidence suggests that this does not completely behave as a common RAFT agent as it is not completely consumed during the polymerization reaction, and it needs atypical high molar ratios [initiator]/[CTA] to be closer to the predicted molecular weight without affecting the Đ. This work demonstrates that MMA and other methacrylic monomers can be polymerized in a controlled way, and with “living” characteristics, using certain symmetrical trithiocarbonates.

Visible-Light Photocatalytic Oxidation of DMSO for RAFT Polymerization.

The solvent is an important, yet often forgotten part of a reaction mechanism. Many photochemical polymerizations are carried out using dimethyl sulfoxide (DMSO) as a way to promote the solubility of both the reactants and products, but its reactivity is rarely considered when initiation mechanisms are proposed. Herein, the oxidation of DMSO by an excited-state quinone is used to form initiating radicals resulting in the polymerization of methacrylate monomers, and the polymerization can be controlled with the addition of a chain transfer agent. This process leads to the formation of polymers with narrow molecular weight distribution, and the polymerization is able to be carried out in the presence of oxygen. A visible light absorbing substituted anthraquinone is synthesized, and nanosecond transient absorption spectroscopy is used to monitor the intermediates involved in the initiation mechanism. Photoproduct analysis indicates formation of methyl radicals as a result of DMSO oxidation. Furthermore, we show that the solvent outcompetes the chain transfer agent for interacting with the excited-state anthraquinone. These observations have a broad impact on photoinduced polymerizations performed in DMSO as many photocatalysts are strong oxidants in the excited state and are capable of reacting with the solvent. Therefore, the role of the solvent needs to be more carefully considered when proposing mechanisms for photoinduced polymerizations in DMSO.

Radical polymerization of methacrylic esters involving various tin(IV) monocathecholate complexes

The effect of tin(IV) monocathecholate 36CatSnR2•nTHF (36Cat is 3,6-di-tert-butylcatehol dianion; R = Me, Et, Ph, or Cl; n = 1 and 2) on the radical polymerization of methyl methacrylate and {itn}-butyl methacrylate was studied. The role of the complexes in the synthesis of the corresponding polymers is mainly determined by the structure of tin o-semiquinone derivatives formed directly in the polymerization process. Tin(IV) monocatecholates can control the synthesis of polymers via the mechanism of reversible inhibition and, in certain cases, exert an accelerating effect on the polymerization of methacrylic monomers like Lewis acids.

Synthesis and Characterization of End-Linked Amphiphilic Copolymer Conetworks Based on a Novel Bifunctional Cleavable Chain Transfer Agent

A novel bifunctional bis(hemiacetal ester) chain transfer agent (CTA), 1,2-bis[1-(4-cyano-4-methyl-1-oxo-4-(phenylcarbonothioylthio)butanoxy)ethoxy]ethane (CMPTBEE), appropriate for the reversible addition–fragmentation chain transfer (RAFT) polymerization of methacrylate monomers, was successfully synthesized and used for the preparation of a family of 10 hydrolyzable end-linked polymer (co)networks. The family comprised three methyl methacrylate (MMA) homopolymer networks with different degrees of polymerization, 100, 150, and 200, and seven end-linked amphiphilic polymer conetworks of MMA and 2-(dimethylamino)ethyl methacrylate (DMAEMA) with a constant overall degree of polymerization equal to 200 but various compositions and architectures. The agreement of the experimentally measured molecular weights with the theoretically expected ones and the low molecular weight dispersities of the linear precursors to the (co)networks indicated successful control of the polymerization. All (co)networks were characterized in terms of their sol fraction and in terms of their degree of swelling in THF. The value of the former was found in the range between 4 and 50%, whereas that of the latter was around 13%. The presence of the hemiacetal ester groups allowed the hydrolysis of the most hydrophilic, DMAEMA-rich conetworks. The resistance to hydrolysis of the other (co)networks could be attributed to the large hydrophobic blocks surrounding and protecting from hydrolysis the hemiacetal ester groups of the CTA residue in the conetworks.

Setting Reaction of Polyacid Modified Composite Resins or Compomers

The hardening of modified polyacid composite resins (compomers) and glass-ionomers have been studied using infrared spectroscopy. The acid-base reaction in Ketac-fil, a glass ionomer, was followed by the ratio between the COOH band located around 1715 cm-1 and that corresponding to COO- located around 1570 cm-1. The combination of infrared analysis and band narrowing treatments enable us to propose in the glass-ionomer two maturation steps. First, a very rapid equilibrium acid-base related, and second the cross-linking of polycarboxylate with the metal ions present in the cement. In compomers, a new reaction has been described involving polymerization induced by free radicals besides the two steps associated with the acid-base reaction. Using infrared spectroscopy and band narrowing techniques, it is shown that water is essential to complete the hardening process but no acid-base reaction is produced since the COO- band does not appear. The reaction associated with free radicals could be described as a polymerization of methacrylate monomers together with an aqueous dilution of the filling particles releasing different metal cations that would chelate with the polymer molecules to form a macromolecular structure.

Preparation of alginate-polymethacrylate hybrid material by radical polymerization of cationic methacrylate monomer in the presence of sodium alginate

An alginate-polymethacrylate hybrid material was prepared by radical polymerization of a cationic methacrylate monomer, i.e. 2-aminoethyl methacrylate hydrochloride in the presence of sodium alginate in water. The insoluble material was formed with progress of the polymerization. The structure of the product was confirmed by the IR spectrum and elemental analysis, as well as the acid hydrolysis experiment to be composed of alginate and polymethacrylate. The TG and DSC data of product were different from those of a mixture of sodium alginate with poly(2-aminoethyl methacrylate hydrochloride). Furthermore, the films of the hybrid materials could be formed by means of the polymerization of the methacrylate monomer in the presence of sodium alginate, followed by the evaporation of the solvent.

Photoinitiated polymerization of methacrylic monomers in a polystyrene matrix: Kinetic, mechanistic, and structural aspects

Photoinitiated polymerization of methacrylic monomers in a polystyrene matrix: Kinetic, mechanistic, and structural aspects

THe Synthesis of Graft, Block, and Star Polymers Using Enolate-Initiated Anionic Polymerization

Initiation of the polymerization of methacrylate monomers by enolate ions affords broad opportunities for the design of several types of macromolecules. Alone, or in combination with other techniques, enolate initiation provides routes to the preparation of well-characterized graft copolymers, block copolymers (of both AB and BAB types), star polymers, and H-polymers. The general mechanism of polymerieation initiated by lithiated esters and silyl ketene acetals is discussed, and examples are presented of the synthesis of each of the kinds of polymer molecules mentioned above

Diminishing Discoloration in Methacrylate Accelerator Systems

To improve color stability in methacrylate accelerator systems, a comparison was made of systems of chemical compounds used in the polymerization of methacrylate monomers at room temperature. This paper reports the tendency of these compounds to form discolored products.