Commercial Monomers Research Articles

Synthesis and stability study of dental monomers containing methacrylamidoethyl phosphonic acids

AbstractThree new dental monomers containing methacrylamidoethyl phosphonic acids were synthesized. The structures of the synthesized monomers were determined with electrospray mass spectrometry (ESMS), Fourier transform infrared, and NMR. The hydrolytic stabilities of the synthesized monomers and a commercial monomer, 2‐methacryloyloxyethyl phosphoric acid (MEP; used as a control), were studied with flow injection (FI)/ESMS, 1H NMR, and 31P NMR analysis of a CD3OD/D2O (4:1 v/v) solution of each monomer before and after storage at 60 °C for 2 months. The 1H NMR and 31P NMR chemical shifts of the monomers 2‐methacrylamidoethylphosphonic acid (I) and N,N′‐[4,4′‐(propane‐2,2‐diyl)‐bis(phenoxy‐2‐hydroxypropyl)]‐bis(2‐methacrylamidoethylphosphonic acid) (II) showed little change after storage at 60 °C for 2 months, but those of MEP changed significantly. FI/ESMS also showed that MEP was nearly completely decomposed, whereas monomers I and II remained largely intact. MEP could react with H2ZrF6 to form ternary zirconium fluoride complexes that were partially soluble in methanol, but all the monomers containing phosphonic acids formed precipitates. This study demonstrates that ESMS is a more sensitive and effective method than NMR for studying the hydrolytic stability or degradation of dental monomers. The new monomers containing methacrylamidoethyl phosphonic acids have higher hydrolytic stability than methacrylate phosphate monomers and may be used in dental bonding agents and other dental materials. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 99–110, 2007

Effects of cis–trans isomerization on the photopolymerization behavior of N-vinyl amide monomers

Photopolymerization behavior of three commercially available N-vinyl amide monomers was compared in air and nitrogen. Additionally, a series of N-substituted N-vinyl formamides was synthesized and their reactivities under photolytic initiation conditions (1 mol% 2,2-dimethoxy-2-phenylacetophenone (DMPA) at 40°C) were studied. Of the five derivatives synthesized, only the benzyl derivative and the N-vinyl formamide (NVF)/methacrylate derivative showed any reactivity toward free radical bulk photopolymerization. It was determined by 13C-NMR analysis that, while the more reactive NVF exists predominantly in the trans conformation with respect to the planar C–N amide bond, the cyclic commercial monomers and the N-substituted derivatives of NVF exist totally or mostly in the cis conformation. The increased cis isomer content has a deleterious effect on polymerization. The cis amide bond is less reactive due to electronic and steric hindrance around the propagating radical center, and the predominance of this isomer leads to low overall reactivity to photolytically catalyzed bulk polymerizations of these monomers.

Synthesis and characterization of highly amine functionalized mesoporous organosilicas by an “all-in-one” approach

Mesoporous organosilicas (MOs) represent a promising class of organic–inorganic nanocomposites for a broad range of applications like catalysis, sensing, separation, or microelectronics. Their distinct feature is the presence of organic groups incorporated into the channel walls of a mesoporous structure. Here, we present a convenient “all-in-one” approach using silsesquioxane surfactant precursors for the functionalization of the channel walls with primary amine groups. The monomer is made by a hydroboration/aminolysis sequence on the base of a commercial monomer, with the template bound to the functionalization site by hydroboration and released after silica condensation and aminolysis. This combination ensures both the placement of the amine groups exclusively along the channel interface as well as optimal use of the template.

Enantiomeric Specificity of Methylsulfonyl-PCBs and Distribution of Bis(4-chlorophenyl) Sulfone, PCB, and DDE Methyl Sulfones in Grey Seal Tissues

PCB methyl sulfones (MeSO2-PCBs) are lipophilic PCB metabolites of which five of the environmentally relevant meta/para pairs are chiral (i.e., exist as atropisomeric pairs). Methylsulfonyl-DDE (MeSO2-DDE) is a DDE metabolite, while bis(4-chlorophenyl) sulfone (BCPS) is a commercial monomer used for thermoplastic production. All these sulfones are well-known environmental contaminants. In this study, liver, lung, and adipose tissue in grey seals (Halichoerus grypus) from the Baltic Sea, naturally exposed to organochlorines via their food, were analyzed for the compounds mentioned. MeSO2-PCBs, 3-MeSO2-DDE, and BCPS were all found in significantly higher concentrations in the liver than in lung and blubber. Their strong liver retention, represented by a median of 42 microg/g l.w. of sigmaMeSO2-PCBs, has previously been mainly neglected in assessments of exposure. The highest concentrations of PCBs and DDE were still found in the grey seal blubber. The atropisomeric composition of MeSO2-PCB congeners was determined, and their enantiomeric fractions were calculated and compared in blubber, liver, and lung tissues. The enantiomeric specificity was equal in all tissues. A notably high abundance (>94%) was observed for one atropisomer in each chiral MeSO2-PCB pair. The first eluting atropisomer (A1) was dominating for all para-substituted MeSO2-PCBs studied, while the second eluting atropisomers (A2) were as dominant in all meta-substituted MeSO2-PCBs in all samples analyzed. In the liver, as much as 50% of sigmaMeSO2-PCBs consisted of the second eluting atropisomer (A2) of 5-MeSO2-CB149. The results imply that the sulfone group is crucial for the specific liver retention of MeSO2-PCBs, 3-MeSO2-DDE, and BCPS.

Synthesis and photopolymerizations of new hydroxyl-containing dimethacrylate crosslinkers

Abstract Two new hydroxyl-containing di(meth)acrylate monomers were synthesized from the reaction of methyl α-chloromethylacrylate (MCMA) and of ethyl α-chloromethylacrylate (ECMA) with glycerol. The monomers were obtained as mixtures of two isomers in different ratios and in combination with the analogous trimethacrylate monomers. Each monomer was isolated by column chromatography. The photopolymerization of these isomer mixtures and the trimethacrylate monomers was investigated individually by photodifferential scanning calorimetry (photoDSC) at room temperature using 2,2′-dimethoxy-2-phenyl-acetophenone (DMPA) as a photoinitiator. The effect of hydrogen bonding on the rates of polymerizations and conversions was examined. The results obtained for the synthesized monomers were compared to the values obtained for commercial monomers. It was observed that the hydroxyl-containing dimethacrylates polymerize much faster and to considerably higher conversion than the trimethacrylate monomers. The maximum rates of polymerization of the hydroxyl-containing monomers were higher than that of the hexanediol dimethacrylate (HDDMA), comparable to glycerol dimethacrylate and lower than hexanediol diacrylate (HDDA) and 3-(acryloyloxy)-2-hydroxypropyl methacrylate (AHM).

Toward self‐assembling dendritic macromolecules from conventional monomers by a combination of living radical polymerization and irreversible terminator multifunctional initiator

AbstractTERMINI stands for irreversible terminator multifunctional initiator and represents a new concept elaborated in our laboratory for the design of novel macromolecules with complex architecture from a diversity of commercial monomers. TERMINI is a masked multifunctional initiator that quantitatively interrupts a living polymerization. After demasking, the TERMINI‐derived repeat unit provides access to a quantitative reinitiation of the same living polymerization in more than one direction, thus becoming a branching point. In this article, with a combination of self‐regulated metal‐catalyzed living radical polymerization and TERMINI, we demonstrate a new method for the divergent synthesis of dendritic poly(methyl methacrylate) containing a bifunctional core at its focal point. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 505–513, 2004

Control of polymer topology through late‐transition‐metal catalysis

AbstractAn Erratum has been published for this article in J Polym Sci Part A: Polym Chem (2004) 42 213In this article, recent examples are reviewed of late‐transition‐metal catalysis applied to polymer topology control. By the judicious selection or design of late‐transition‐metal catalysts, polymers with a broad range of topologies, including linear, short‐chain‐branched, hyperbranched, dendritic, and cyclic topologies, have been successfully synthesized. A distinctive advantage of the catalyst approach is that polymers with complex topologies can be prepared in one pot from simple commercial monomers. A fundamental difference of the catalyst approach with respect to other approaches is that the polymer topology is controlled by the catalysts instead of the monomer structure. In our own laboratory, we have successfully used two strategies to control the polymer topology with late‐transition‐metal catalysts. In the first strategy, hyperbranched polymers are prepared by the direct free‐radical polymerization of divinyl monomers through control of the competition between propagation and chain transfer with a cobalt chain‐transfer catalyst. In the second strategy, polyethylene topology is successfully controlled by the regulation of the competition between propagation and chain walking with the Brookhart PdII‐α‐bisimine catalyst. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3680–3692, 2003

Universal iterative strategy for the divergent synthesis of dendritic macromolecules from conventional monomers by a combination of living radical polymerization and irreversible TERminator multifunctional INItiator (TERMINI).

A new synthetic concept named TERMINI that stands for irreversible TERminator Multifunctional INItiator is reported. Suitable combinations of TERMINI and living polymerizations provide access to strategies for the design and synthesis of unprecedented complex molecular and macromolecular architectures from a diversity of commercial monomers. TERMINI represents a masked multifunctional initiator designed to quantitatively and irreversibly interrupt a chain organic reaction or a living polymerization. After demasking, the TERMINI repeat unit enables the quantitative reinitiation, in the presence or absence of a catalyst, of the same or a different living polymerization or a chain organic reaction in more than one direction, thus becoming a branching point. The demonstration of this concept was made by using a combination of metal-catalyzed living radical polymerization (LRP) and (1,1-dimethylethyl)[[1-[3,5-bis(S-phenyl 4-N,N'-diethylthiocarbamate)phenyl]ethenyl]oxy]dimethylsilane as TERMINI, to elaborate a novel iterative divergent method for the synthesis of dendritic macromolecules based on methyl methacrylate (MMA).

Methacrylate derivatives incorporating pyroglutamic acid.

Methacrylates containing pyroglutamic acid were synthesized in good yields. Methyl alpha-pyroglutamyl methylacrylate (PyMM) and methyl alpha-pyroglutamidoundecanoyl methylacrylate (PyUM) give very fast photopolymerization rates both in homopolymerizations and with widely used commercial monomers N-vinyl pyrrolidinone (NVP) and hydroxyethyl methacrylate (HEMA). Soluble or cross-linked homopolymers can be obtained depending upon polymerization temperature. Pyroglutamic methacrylates polymerize without added initiator in the melt. Solution cast, photocured, and thermally cured coatings gave good to excellent adhesion to poly(ethylene terephthalate) and glass surfaces.

Characterization of UV‐curable reactive diluent containing quaternary ammonium salts for antistatic coating

AbstractReactive diluent with quaternary ammonium salts (RDQ) for UV‐curable antistatic coating was synthesized by reacting glycidyl methacrylate (GMA) and piperazin with dropping the methansulfonic acid. In order to compare the curing behavior of RDQ with commercial monomers, the photopolymerization of RDQ, 1,6‐hexandiol diacrylate (HDDA) and 1,6‐hexandiol dimethacrylate (HDDMA) were studied by using real‐time IR spectroscopy. Surface properties such as surface resistance, pencil hardness, and solvent resistance of the cured films containing RDQ were investigated. When used as a reactive diluent in the UV‐curable coating formulation, the RDQ imparted excellent antistatic properties to the final material. The results of an Fourier transform infrared/attenuated total reflectance (FTIR/ATR) depth profile analysis show that RDQ molecules are more concentrated near the surface within a micrometer‐thick layer, indicating that existence of the ionic components in the surface layer is responsible for antistatic property. Film cured from the formulation containing 12 wt % of RDQ showed the best mechanical properties with reasonable surface properties. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 132–137, 2002; DOI 10.1002/app.10273

Uma demonstração simples e visual do efeito do aquecimento com microondas em reações de poliadição

Polyaddition of commercial monomers is easily performed on a domestic microwave oven. The rate of polymerization depends on the structure of the monomer, power and time of irradiation. This methodology can easily be used to demonstrate the acceleration of organic reactions promoted by microwaves.

New N-Halamine Biocidal Polymers

A new series of N-halamine polymers has been synthesized and tested in granular form, on glass and as fiber substrates for efficacy at inactivating bacteria. Copolymers and grafted copolymers were prepared with 4-(alkyl acryloxymethyl)-4-ethyl-2-oxazolidinones and commercial monomers or polymers. These polymers are inexpensive to synthesize and are efficient biocides in granular form and as surface-coated disinfectants. They can be coated on glass, plastic, and fibrous materials, which gives them considerable potential as commercial disinfectants. They could be used for a variety of industrial, commercial, and medical applications.

“Sugar Diols” as Building Blocks of Polycondensates

The term sugar diols is used throughout this review as a nickname for diols that are usually derived from saccharides. Typical examples of such “sugar diols” are the bicyclic ethers L-sorbitol (A), L-iditol (z), and L-mannitol (3),—where 1 and 1 are commercial monomers. Furthermore, the acetals 4, 5, 6, and 7 should be mentioned, which are all commercial. These sugar diols have recently attracted increasing interest as monomers for the synthesis of various polycondensates. Several reasons are responsible for this tendency. 1. All sugar diols can be prepared from saccharides (although other synthetic routes may also be available) and thus are monomers based on renewable resources. 2. Most sugar diols (e.g., 1–4 and 7) are nontoxic and their polyesters derived from aliphatic dicarboxylic acids are sensitive to hydrolysis. Such aliphatic polyesters will degrade in the course of several months in contact with warm neutral water and thus are considered to be useful biodegradable materials. 3. All sugar diols are chiral and belong to the least expensive chiral monomers (particularly 1). Potential applications of chiral polymers concern membranes, stationary phases for chromatography, and, above all, cholesteric oligomers and polymers. 4. Isosorbide (L-sorbitol) is a chemically and thermally unusually stable aliphatic diol. As discussed below, polyesters derived from 1 do not racemize or decompose when heated for a few minutes to temperatures up to 350°C.

Decomposition analysis of binary polyfunctional urethane monomer mixtures.

Thermal decomposition in three binary monomer mixture systems containing an experimentally synthesized monomer (EXP3) and a commercial polyfunctional urethane monomer (U-4TXA) was examined in terms of differential thermal analysis (DTA) and simultaneous thermogravimetry (TG) analysis when a sample was heated to 800 degrees C. The binary EXP3/U-4TXA monomer mixtures were visible light-cured (VLC) resins which included CQ (camphorquinone=0.5 wt%) and DMAEMA (dimethylaminoethyl methacrylate=0.5 wt%) as the photoinitiator. Their DTA curves showed that thermal decomposition initiated at around 300 degrees C and finished at around 500 degrees C. TG curves showed complete weight loss at 800 degrees C during thermally induced decomposition: the decomposition reaction at weight losses of 5 to 50% was calculated from the slope of the (1/T) versus log10(Hr) diagram, because the exothermic decomposition temperature shown on DTA curves increased with increasing heating rate from 2 to 20 degrees C/min. Thermal decomposition analysis showed that a decomposition with weight change had exothermic heats ranging from 0.38 to 1.07 kJ/g for the EXP U1 mixture, 1.06 to 1.76 kJ/g for EXP U2 and 1.74 to 2.02 kJ/g for EXP U3. Activation energy ranged from 1.42 to 1.89 kJ/mol at weight losses of 5 to 50% in the three binary EXP3/U-4TXA monomer mixture systems.

Surface photografting of low-density polyethylene films and its relevance to photolamination

Surface modifications of pristine and ozone-pretreated low-density polyethylene (LDPE) films were carried out via UV-induced graft copolymerization with a photoinitiator-containing, epoxy-based commercial monomer (DuPont Somos™ 6100 for solid imaging and optical lithography) and also with the photoinitiator-free acrylic acid (AAc). The chemical composition and microstructure of the graft copolymerized surfaces were studied by angle-resolved X-ray photoelectron spectroscopy (XPS). The concentration of surface grafted polymer increased with the UV illumination time and the monomer concentration. For LDPE films graft copolymerized with the epoxy-based monomer, surface chain rearrangement was not observed or was less well pronounced, due to the partial crosslinking of the grafted chains. Simultaneous photografting and photolamination between two LDPE films, or between a LDPE film and a poly(ethylene terephthalate) (PET) film, in the presence of either monomer system, were also investigated. The photolamination rates and strengths depend on the ozone pretreatment time, the UV illumination time, and the UV wavelength, as well as on the nature of the substrate materials. A shear adhesion strength approaching 150 N/cm2 could be achieved with either monomer system, provided that the polymer films were pretreated with ozone. The failure mode of the photolaminated surfaces was cohesive in nature in the case of the photoinitiator-containing epoxy monomer, but was either cohesive or adhesional in nature (depending on the substrate assembly) in the case of the photoinitiator-free AAc monomer.

Ring‐opening metathesis polymerization of 9‐phenyl‐1,5‐cyclododecadiene

AbstractSynthesis of butadiene‐based sequence‐controlled copolymers that are composed of commercial monomers such as styrene, butadiene, and ethylene was investigated. New substituted cyclododecadiene derivatives, 9‐phenyl‐1,5‐cyclododecadiene was synthesized by reductive‐phenylation method from 1,5‐cyclododecadiene‐9‐one and was polymerized with tungsten‐based catalyst systems to obtain a microstructure‐controlled terpolymer. A sequence‐controlled 2 : 1 : 1 terpolymer of butadiene, styrene and ethylene was successfully synthesized. The glass transition of the terpolymer occurred at −33.6°C. © 1995 John Wiley & Sons, Inc.

Studies on certain wood-plastic-composites prepared by gamma irradiation

Wood-plastic-composites have been prepared using locally available soft wood and commercial monomers by vacuum impregnation of monomer in wood and subsequent polymerization by gamma irradiation. The irradiation was performed by means of a60Co source of strength 50,000 Ci at 0·2 Mrad/h. The radiation dosage required for maximum conversion of monomer into polymer was less than 2 Mrad except styrene which required a much larger dose of about 10 Mrad. The impregnation efficiency was found to be more for wood with high pore volume. The impregnation efficiency also depended on the ambient pressure: the more the vacuum, the more was the impregnation efficiency. Mechanical strength of the composites was found to be enhanced and water absorption considerably reduced. X-ray diffraction studies showed that the crystallinity of the cellulose did not get affected by the radiation polymerization which suggested that grafting of polymer on to the cell wall took place only in the amorphous regions.

Bulk radical homo-polymerisation studies of commercial acrylate monomers using near infrared Fourier transform Raman spectroscopy

In our previous work we have used near infrared Fourier transform Raman spectroscopy to provide a reliable, reproducible and quantitative method for in situ reaction monitoring of homo-polymerisation. Model systems such as styrene and methylmethacrylate were studied. In this present work three commercial monomers have been studied, namely butylacrylate, hydroxylpropylmethacrylate and laurylmethacrylate. The effects of reaction temperature, monomer additives and the presence of oxygen have been elucidated. These reaction variables have been shown to have a significant effect on polymerisation rate in particular for the butylacrylate system.

Visible light cured resin. Chronological change in mechanical properties of matrix resin immersed in MeOH

Monomer composition was examined to improve durability of matrix resin of visible light cured composite resin. As a monomer, five kinds of cyclophosphazene monomers, two kinds of commercial monomers and a mixture of commercial monomers were prepared to the visible light cured resins. The mechanical properties of these set products were examined with time after immersion in MeOH, an aging accelerating solvent. Compressive strength of the resins using cyclophosphazene monomers tended to decrease with time, but it increased in accordance with the increase of the number of polymerization group. Compressive strength of the resins using commercial monomers tended to decrease, but that using the BMPEPP monomer tended to increase with time. Yield point of the resins with the cyclophosphazene monomer 4 PN-(EMA)8 tended to increase with the time but that of the resins with other cases monomers decreased. The yield point of all three resins made using commercial monomers tended to decrease with time, but the rate of decrease was small for BMPEPP monomer. Compressive elastic modulus of the resins using cyclophosphazene monomers tended to increase with time when the number of polymerization group was 6-8, while it decreased when the number was 4-5. When commercial monomers were used, it tended to decrease with time, but the rate of decrease was small for the BMPEPP monomer. Transverse strength of the resins using cyclophosphazene monomers showed a tendency to decrease with time. When a commercial monomer was used, cracks appeared in the Bis-GMA+Tri-EDMA monomer after 7 days, and with the other two monomers, the transverse strength tended to decrease with time, though the rate of decrease was small for the BMPEPP monomer. Transverse elastic modulus tended to decrease with time, but the rate of decrease was small for the BMPEPP monomer.

可視光線重合型レジンの吸水量, 溶解量および膨潤量 : シクロホスファゼンモノマーおよび市販モノマーを用いたレジンについて

Studies were done to decrease both the water sorption and solubility of visible light cured resin. As monomer, three kinds of cyclophosphazene monomers and three kinds of commercial monomers were prepared to the visible light cured unfilled resins. When these set products were immersed in water, MeOH and THF, water sorption and solubility in water, MeOH sorption and solubility in MeOH, THF sorption, and mechanical properties were examined. Water sorption was increased by degrees for all the monomers. In the cases of 4 PN-(EMA)8, 4 PN-(TF)1-(EMA)7, 4 PN-(TF)2-(EMA)6, Tri-EDMA, BMPEPP and Bis-GMA + Tri-EDMA, the value of solubility in water after 30 days, was 0.16, 0.20, 0.51, 0.65, 0.17 and 0.81% respectively. MeOH sorption showed a tendency to increase, except for Bis-GMA + Tri-EDMA and 4 PN-(TF)2-(EMA)6. Solubility in MeOH after 30 days, for cyclophosphazene monomers and commercial monomers, was 0.09-0.36% and 1.36-5.40%. THF sorption after 30 days, for cyclophosphazene monomers, was small in comparison with that of commercial monomers. Compressive strength was 230-275 MPa in all cases. But, transverse strength, for all the cyclophosphazene monomers, was 45 MPa or below. In the cases of commercial monomers, the value of transverse strength was 55-90 MPa.