Emulsion polymerisation of highly water-insoluble monomers

Contrary to an earlier report, monomers (e.g. p-tert-butylstyrene and octadecyl methacrylate) which are less soluble in water than styrene have been found to polymerise in emulsion using persulphate initiation. At 60°C, the order of the Interval II polymerisation rate of octadecyl methacrylate is 0.48 in persulphate concentration and 0.68 in sodium dodecyl sulphate concentration. The rate is increased by addition of methanol to the aqueous phase. Unlike styrene, p-tert-butylstyrene could not be polymerised in aqueous suspension by persulphate in the absence of emulsifier. High emulsifier-monomer ratios were used in these experiments so that it is possible that mini-emulsion droplets were a significant reaction locus.     

Composite resins based on novel and highly reactive bisglycidyl methacrylate monomers

Three new bisglycidyl monomers; 1,4‐bis((2‐hydroxy‐3‐methacryloxypropoxy) methyl)benzene (MB‐Phe‐OH), 1,4‐bis(2‐hydroxy‐3‐methacryloxypropoxy)2‐cis‐butene (MB‐Cis‐OH), and 1,7‐bis(2‐hydroxy‐3‐methacryloxypropoxy)heptane (MB‐1,7‐OH); were synthesized and used as Bis‐GMA/TEGDMA (bisphenolglycidyl methacrylate/triethylene glycol dimethacrylate) composite resin additives. Flexural properties and double bond conversion of the dental resins composed of silanizated inorganic filler and organic matrices containing new monomers were evaluated. The composite resins formulated, using the monomers MB‐Cis‐OH and MB‐1,7‐OH, have mechanical properties and double bond conversion comparable with those of Bis‐GMA/TEGDMA composite resin used as control. The composite containing the new monomer MB‐Phe‐OH has better flexural properties (flexural strength 65.01 MPa and flexural modulus 5675.91 MPa) than the control composite resin (flexural strength 52.85 MPa and flexural modulus 4879.72 MPa); this could be attributed to the molecular structure of the monomer and its high double bond conversion level of 74.19%. The new bisglycidyl methacrylate monomer MB‐Phe‐OH could be potentially useful in the development of new organic matrices for dental composite resins with high double bond conversion and enhanced mechanical properties. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40971.     

Synthesis and cationic photopolymerization of fluorine‐containing vinyl ether monomers for the hydrophobic films

Fluorine‐containing vinyl ether monomer is a combination of UV‐curing technology and low surface energy materials. In this article, a type of fluorine‐containing vinyl ether monomer was synthesized by the reaction of fluorinated alcohols, hexafluorobenzene, 2‐vinyloxy ethanol, and sodium hydride. These monomers exhibit low viscosity and good fluidity. The effect of the fluorine content of the monomers on their UV‐curing behavior was monitored by photo‐differential scanning calorimetry. The photo‐polymerization process was efficient because the double‐bond conversed sufficiently (>85%) and the curing rate was fast (<20 s). In addition, the surface energy of homopolymer and copolymer films was researched. The surface free energy was very low and could even reach 0.92 mJ m^?2. The low surface energy was due to high fluorine content and the diffusion of uncured monomers, which was on the basis of X‐ray photoelectron spectroscopy data and observed conversions. The structure of homopolymers and copolymers was one of the most important influences on the surface free energy and the thermal properties. The copolymers exhibited better thermal stability than the homopolymers. All of these results demonstrated that these monomers are suitable for a wide range of practical applications such as UV coatings, UV inks, and photoresists. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41019.     

A kinetic study of the acceleration effect of substituted benzyl alcohols on the cationic photopolymerization rate of epoxidized natural oils

The rate of the cationic photopolymerization of epoxidized natural oils was enhanced by the addition of several mono, di and trisubstituted benzyl alcohols. The epoxidation of vegetable oils was achieved by using 30% hydrogen peroxide with methyl trioxo rhenium (MTO) as a phase transfer catalyst. Then, the effect of different methoxy-substituted benzyl alcohols on the curing rate was evaluated, using the real-time FT-IR technique. The overall result was an increase in the curing rate. The acceleration effect was explained on the basis of synergistic effects of two mechanisms, namely, the radical induced cationic photopolymerization and the activated monomer mechanism. Epoxidized oils with 2,5-dimethoxybenzyl alcohol as an accelerator exhibited the highest photopolymerization rate. Higher conversions were obtained using electron-transfer photosensitizers.     

Synthesis and photopolymerization of phosphonic acid monomers for applications in compomer materials

Novel methacrylate monomers bearing phosphonic acid groups 1 and 2 as well as new sulfur methacrylates 9 and 10 have been prepared in good yields from thiophenol. They have been fully characterized by ¹H‐NMR, ¹³C‐NMR, ³¹P‐NMR, and HRMS. Their copolymerization with a bis‐GMA : TEGDMA (1 : 1) blend has been investigated with photodifferential scanning calorimetry at 50°C with camphorquinone as a photoinitiator and ethyl 4‐(dimethylamino)benzoate (EDAB) as a coinitiator. The higher the content of acidic monomer 1 or 2 incorporated in the bis‐GMA : TEGDMA (1 : 1) blend, the lower the mixtures reactivity. The phosphonic acid group has been proved to be responsible for this drop of reactivity. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and cationic photopolymerization of a new fluorinated oxetane monomer

A new fluorinated oxetane monomer (FOX) was prepared using a fluorinated alcohol by phase transfer catalysis in a Williamson ether synthesis. The new fluorinated monomer was used in cationic photopolymerization as comonomer of 3,3′-[oxydi(methylene)]bis(3-ethyloxetane). The presence of the FOX monomer induces a decrease of the glass transition temperature, thermal stabilization and an increase of the final oxetane group conversion. Completely hydrophobic surfaces were obtained with a selective enrichment of the fluorinated comonomer, as confirmed by contact angle and XPS analysis.     

NIR‐laser based detection of the photopolymerization state of acrylate coatings suitable for in situ measurements

The present article describes a method for the determination of the radical photopolymerization conversion of acrylic coatings suitable for an in situ monitoring during the coating process. Acrylate based coatings are increasingly used in many kinds of industrial coating processes, because of advantages of the solvent‐free application process. The applied method is based on 1620 nm light absorption of the acrylate. To overcome the disadvantages of a common NIR spectrometer, only the diffuse reflection of the relevant discrete wavelength at 1620 nm and of a reference wavelength is measured. A sophisticated sensor setup including an optical spatial filter and lock‐in amplified signal processing is used to achieve a sufficient signal to noise ratio. The capability of the sensor to discriminate between polymerized and unpolymerized coatings on metal substrates down to a coating thickness of 16 μm is demonstrated. Furthermore, the information on polymerization from larger depth in TiO₂ pigmented coatings is investigated. The results can be analytically modeled in analogy to the Lambert–Beer's law, resulting in a detection limit of a maximum pigment concentration of 15 wt % with 100 μm coating thickness. The presented sensor design is suitable to be used in an industrial production environment for example in screen printing applications as a monitoring and quality control tool. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

A novel ferrocenium salt as visible light photoinitiator for cationic and radical photopolymerization

A novel hybrid photoinitiator for visible light photopolymerization, (η⁶-3-benzoyl-4-chlorodiphenylamine) (η⁵-cyclopentadienyl) iron hexafluorophosphate (Fc-NBP), was synthesized and studied. Its absorption in the UV and visible light regions showed much stronger activity than those of either the commercialized cationic photoinitiator I-261 or the conventional free radical photoinitiator benzophenone, especially above wavelengths of 350 nm. When exposed to visible light, the photoinitiator under study initiates both cationic polymerization and radical polymerization. The photoinitiator's abilities in the photopolymerization of acrylates and epoxides were evaluated by near infrared (NIR) spectroscopy. The results from NIR clearly indicate that Fc-NBP exhibited high efficiency in photopolymerizing acrylate monomers. In the same lamp, however, benzophenone showed no photoinitiating ability. The photopolymerization rate of the diglycidyl ether of the bisphenol-A epoxy (DGEBA) oligomer was found to be slower than that of acrylates when using Fc-NBP as the photoinitiator. This study shows that the polymerization of epoxide DGEBA can be speeded up by adding a photosensitizer benzoyl peroxide (BPO), but BPO and tertiary amines do not affect the free radical photopolymerization of tripropylene glycol diacrylate (TPGDA). We conclude by providing a possible photoinitiation mechanism.     

一种新型阳离子聚丙烯酰胺的合成及表征

将具有球型分子结构的超支化聚合物接枝到阳离子聚丙烯酰胺上,目的是当用阳离子聚丙烯酰胺处理油田污水时,抑制分子的卷曲速度,提高絮凝性能。作者首先以二甲基二烯丙基氯化铵(DMDAAC)、丙烯酰胺(AM)和丙烯酸(AA)为单体,聚合得阳离子聚丙烯酰胺,该聚合物具有线型分子结构。再以甲基丙烯酰氧乙基三甲基氯化铵(DMC)与端部氨基的超支化聚合物反应,得到端部带有阳离子的超支化聚合物,该聚合物具有类似球型的分子结构。然后将阳离子超支化聚合物接枝到线形阳离子聚丙烯酰胺上,得到一种接枝改性的阳离子聚丙烯酰胺。用红外分光光度仪分析证明得到了预期的产物结构,并测定了产物的特性粘度、阳离子度。     

Synthesis and cure kinetics of bisoxazoline monomers during cationic ring-opening polymerization

In this work, the synthesis and characterization of highly aromatic bisoxazoline (BOX) monomers containing diphenyl ether, furan, and thiophene backbones are presented. Preliminary investigations of the cure and reaction kinetics are performed to understand the impact of these moieties on polymerization and their glass transition temperatures. To do this, two catalysts are used, methyl triflate (MT) and dodecyl benzene sulfonic acid (DBS) to explore their role in controlling the cationic ring-opening polymerization (CROP) mechanism. Polymerization was monitored using non-isothermal differential scanning calorimetry and characterized according to the Kissinger and Ozawa models. Kinetic modeling using the Malek and Sestak-Berggren methods showed excellent agreement with experimental values and was used to determine reaction rate constants. The polymerization of BOX monomers in the presence of both MT and DBS is shown to be highly latent, being stable until the melting point is reached, after which reaction occurs rapidly.     

A cost-effective process for highly reactive polyisobutylenes via cationic polymerization coinitiated by AlCl3

The initiating system consisting of AlCl₃ with dialkyl ether such as di-n-butyl ether or diisopropyl ether has been successfully developed for providing a cost-effective process of synthesis of highly reactive polyisobutylenes (HRPIBs) with large proportion of exo-olefin end groups up to 93 mol% at temperatures ranging from −20 to +20 °C. The above dialkyl ethers played very important roles in promoting the directly rapid β-proton elimination from -CH₃ of the growing chain ends to create exo-olefin end groups and decreasing or even suppressing the carbenium ion rearrangements to form the double bond isomers. Very importantly, the highly reactive PIBs with 80-92 mol% of exo-olefin end groups, having low M_ns of 1300-2300 g mol⁻¹ and monomodal molecular weight distribution (M_w/M_n = 1.7-2.0) could be achieved at 0-20 °C. These results are comparable to those of commercial HRPIBs produced industrially by the best BF₃-based initiating system at far below 0 °C.     

Synthesis,characterization, and UV‐curing properties of silicon‐containing (Meth)acrylate monomers

Eight different silicon‐containing (meth)acrylate monomers are synthesized by the substitution reaction of chlorosiloxanes with 2‐hydroxyethyl methacrylate or 2‐hydroxyethyl acrylate. Their molecular structures are confirmed by IR, ¹H‐NMR, and ¹³C‐NMR spectroscopic analyses. The effects of silicon content on the UV‐curing behavior, physical, surface, and thermal properties are investigated. The UV‐curing behavior is analyzed by photo differential scanning calorimetry. The surface free energy of the UV‐cured film is calculated from contact angles measured using the Lewis acid‐base three liquids method. The silicon‐containing (meth)acrylate monomers perform much better than traditional (meth)acrylate monomers on UV‐curing. The silicon‐containing monomers have higher final conversions and fast UV‐curing rates in photopolymerization. The surface free energy decreases with increasing silicon content, because silicon in the soft segment is transferred to the surface, producing a UV‐cured film; this is confirmed by X‐ray photoelectron spectroscopy measurements. All these advantageous properties enable these synthetic silicon‐containing monomers to perform better in applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

A novel binder suitable for cationic electrodeposition coatings based on a non-isocyanate chemistry

A non-polyisocyanate resin system that can be applied to cationic electrodeposition (CED) paint has been developed. Most of the compositions of binders currently on the market as CED coatings are composed of modified epoxy resins and blocked polyisocyanates, their crosslinking essentially being polyurethane or polyurea formation. This report deals with a new resin system of which crosslinking is based on a ring-opening/etherification reaction between epoxy groups and hydroxyl groups. The ring-opening addition reaction has very low emissions during the baking process. However, it is difficult to attain a compromise between satisfactory reactivity at elevated temperatures and stability in aqueous composition. By a series of careful investigations, we have established the composition of CED coatings that are sufficiently stable and can be satisfactorily cured. The CED paint formulated on this resin system has such desirable properties as low weight loss upon baking, outstanding weatherability, and excellent chipping resistance. Other characteristics are comparable to existing polyisocyanate based CED coatings.     

Synthesis and characterization of novel organotin monomers and copolymers and their antibacterial activity

Two novel organotin monomers, (N‐tri‐n‐butyltin) maleimide and m‐acryloylamino‐(tri‐n‐butyltin benzoate), were synthesized. Copolymerization of these two monomers with styrene was carried out in the bulk at 65°C using asobisisobutyronitrile as the free radical initiator. The monomers and copolymers were characterized by elemental analysis; the molecular weights of the copolymers were determined by GPC, solubility, IR, and ¹H‐NMR spectral studies. The antibacterial activities of the synthesized organotin monomers and copolymers toward various types of bacteria were also reported. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 740–745, 2000     

Synthesis of novel sulfonium salts and cationic polymerization of epoxides and vinyl ether

Novel 1‐methoxycarbonylethylmethylphenylsulfonium salts with nonnucleophilic anions, namely, hexafluorophosphate, hexafluoroantimonate, and tetrafluoroborate, were synthesized by the reaction of 1‐methoxycarbonylethylphenylsulfide and dimethyl sulfate followed by anion exchange with potassium hexafluorophosphate, sodium hexafluoroantimonate, and sodium tetrafluoroborate, respectively. The cationic polymerization (photopolymerization and thermal polymerization) of epoxy and vinyl ether monomers was carried out to demonstrate the applicability of the newly synthesized sulfonium salts. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3157–3163, 2007     

Study of epoxidized-cardanol containing cationic UV curable materials

Cationic photopolymerization, thermal and mechanical properties of thin film materials containing bio-renewable cashew nutshell oil derivative – epoxidized-cardanol (ECD) were investigated. Higher and more consistent monomer conversion as a function of relative humidity was found for thin film materials containing 10 wt.% ECD and 5 wt.% hydroxy-functional reactive diluents during cationic photopolymerization. In addition, ECD imparted balanced physiochemical properties to the cationic UV curable materials. ECD showed great potential to be used as a reactive ingredient in cationic UV curable materials.     

Synthesis of novel antibacterial monomers (UDMQA) and their potential application in dental resin

To prepare antibacterial dental resin, a series of novel urethane dimethacrylates quaternary ammonium methacrylate monomers (UDMQAs) with different substituted alkyl chain length were synthesized, and their structures were confirmed by FTIR and ¹H‐NMR spectra. The obtained UDMQAs were used to replace 2,2‐Bis[4‐(2‐hydroxy‐3‐methacryloyloxypropyl)‐phenyl]propane (Bis‐GMA) totally as base monomers of dental resin and mixed with Tri‐ethyleneglycol dimethacrylate (TEGDMA) at the mass ratio of 50/50. The properties of these prepared resins like antibacterial activity, double bond conversion (DC), polymerization shrinkage, flexural strength (FS), and modulus (FM), water sorption and sol fraction were investigated. The most commonly used dental resin Bis‐GMA/TEGDMA (50wt/50wt) was chosen as a reference. The results showed that UDMQAs could endow dental resin with antibacterial activity. Compared with Bis‐GMA‐based dental resin, UDMQAs‐based resin had the same or higher DC, lower polymerization shrinkage, lower flexural strength and modulus, and higher water sorption and sol fraction. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Polymerization behavior of an organophosphorus monomer for use in dental restorative materials

Vibrational overtone activated polymerization of acrylonitrile (AN) has been demonstrated using two initiators, benzoyl peroxide (BP), and 2,2′‐(azobis)isobutyronitrile (AIBN). Excitation of the fifth vibrational overtone of the CH stretch of AIBN at 627 nm and BP at 604 nm initiates the reaction. Monomer conversions were monitored by a gravimetric method. In both cases, the wavelength selectivity was investigated by irradiating the monomer/initiator mixtures at the absorption maximum of the initiator, the absorption maximum of the monomer, and at a wavelength (580 nm for AN/AIBN and 625 nm for AN/BP) where neither the initiator nor the monomer absorbs light. For the AN/AIBN mixture, after 48 h the monomer conversion for the irradiation on the peak absorption of AIBN (627 nm) is about twice as large as the irradiation at 580 nm. For the AN/BP mixture, after 48 h the monomer conversion for the irradiation on the peak absorption of BP (604 nm) is about a factor of 2.2 larger than for the irradiation at 625 nm. The overall quantum yields of both polymerizations were estimated. After 48 h the overall quantum yield for the AN/AIBN mixture irradiated at the initiator absorption (Φ₆₂₇ = 21083) is about 10 times larger than for the sample irradiated at the pure monomer absorption (Φ₅₉₅ = 1942). For the AN/BP mixture, the 604 nm quantum yield (Φ₆₀₄ = 1096) is about 2.4 times larger than the 595 nm quantum yield (Φ₅₉₅ = 448). The influence of the initiator concentration is also presented. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 565–571, 2003     

Synthesis of an oxetane‐functionalized hemispiroorthocarbonate used as a low‐shrinkage additive in the cationic ultraviolet curing of oxetane monomers

The synthesis of an hemispiroorthocarbonate functionalized with an oxetane group is reported. The obtained monomer was used as a slow shrinkable additive in the cationic ultraviolet curing of a commercially available dioxetane resin. We evidenced polymer network flexibilization by increasing the oxetane‐functionalized hemispiroorthocarbonate content in the photocurable formulation. It was demonstrated that spiroorthocarbonate acted as a shrinkage reduction additive and reached expansion on volume after polymerization in the presence of 50 wt % of the functionalized spiroorthocarbonate. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009