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1.
The synthesis of a series of novel cationically photopolymerizable epoxide monomers bearing benzyl, allyl, and propargyl acetal and ether groups that can stabilize free radicals was carried out. These monomers display enhanced reactivity in cationic photopolymerization in the presence of certain onium salt photoinitiators. Specifically, this article describes schemes for the synthesis of cycloaliphatic epoxy monomers bearing free‐radical stabilizing groups. During UV irradiation of an onium salt cationic photoinitiator, the aryl radicals that are generated abstract labile protons present in such monomers to generate the corresponding carbon‐centered radicals. Subsequently, these radicals can interact with the onium salt by a redox mechanism to induce the decomposition of these salts. The overall result is that additional cationic species are generated by this mechanism that increase the rate and extent of the cationic ring‐opening polymerization of the epoxide monomer. An investigation of the photopolymerizations of the monomers prepared during this work was carried out using Fourier transform real‐time infrared spectroscopy, and conclusions were drawn with respect to the relationship between their structures and reactivity. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2385–2395, 2001  相似文献   

2.
Photoinitiated cationic polymerization by photosensitization of diphenyliodonium and triphenylsulfonium salts is shown to proceed by two distinct electron transfer process: (1) direct electron transfer from excited-state photosensitizers and (2) indirect electron transfer from photogenerated radicals. The efficiency of the former process is attributed to the instability of the reduction products (from diphenyliodonium and triphenylsulfonium salts), which dissociate in competition with undergoing energy-wastage reverse electron transfer. Amplification of photons in the production of protons (or other reactive cations) is postulated to account for the high quantum yields observed in the latter process. Potential advantages of utilizing the indirect redox process in the design of UV curable hybrid systems, which contain functionality for both radical and cationic polymerization, are noted. The results also provide evidence against the importance of triplet states of the onium salts in photoinitiator activity.  相似文献   

3.
Phenothiazine compounds bearing a wide range of different substituents are excellent photosensitizers for onium salt cationic photoinitiators. These photosensitizers are generally operative in the mid‐ and long‐range regions of the UV spectrum and are especially useful for enhancing the rate of photoinitiated cationic polymerization carried out utilizing both filtered and broadband UV emission sources. In this article, the syntheses of several different substituted phenothiazines are described and the ability of these compounds to photosensitize the photolysis of different onium salt photoinitiators is evaluated. Attempts were made to correlate the structure and spectral characteristics of the phenothiazines with their efficiency of photosensitization in the cationic photopolymerizations of several typical epoxide and vinyl ether monomers. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1187–1197, 2001  相似文献   

4.
A series of novel, cycloaliphatic, cationically photopolymerizable epoxide monomers bearing benzyl ether groups were prepared. These monomers display a considerable enhancement in the rate of their cationic ring‐opening polymerizations in comparison with monomers that do not contain such groups. In this article, a synergistic free‐radical mechanism is proposed that accounts for this effect, and supporting evidence is offered for its verification. During UV irradiation of an onium salt cationic photoinitiator, the aryl radicals that are generated abstract labile benzyl hydrogens present in such monomers to generate the corresponding carbon‐centered radicals. Subsequently, these radicals are oxidized to benzyl carbocations by the onium salt via a nonphotochemical chain process. The observed increase in the rate and extent of the cationic ring‐opening polymerization of the epoxide monomers is due to the aforementioned mechanism, which effectively increases the number of reactive cationic species present during polymerization. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3578–3592, 2001  相似文献   

5.
A kinetic study was conducted of the independent photoinitiated cationic polymerization of a number of epoxide monomers and mixtures of these monomers with N‐vinylcarbazole. The results show that these two different classes of monomers undergo complex synergistic interactions with one another during polymerization. It was demonstrated that N‐vinylcarbazole as well as other carbazoles are efficient photosensitizers for the photolysis of both diaryliodonium and triarylsulfonium salt photoinitiators. In the presence of large amounts of N‐vinylcarbazole, the rates of the cationic ring‐opening photopolymerization of epoxides are markedly accelerated. This effect has been ascribed to a photoinitiated free‐radical chain reaction that results in the oxidation of monomeric and polymeric N‐vinylcarbazole radicals by the onium salt photoinitiators to generate cations. These cations can initiate the ring‐opening polymerization of the epoxides, leading to the production of copolymers. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3697–3709, 2000  相似文献   

6.
Photoactive allyl ammonium salt (BPEA) containing benzophenone moiety in the structure was synthesized and characterized. Its capability to act as a self-initiating addition fragmentation agent in the photoinitiated cationic polymerization of oxiranes such as cyclohexene oxide and vinyl monomers such as butylvinyl ether was investigated. These monomers turned out to be polymerizable in the presence of BPEA provided free radicals are generated photochemically at λ>300 nm by hydrogen abstraction of excited benzophenone moiety. Accordingly, a free radical adds to the carbon-carbon double bond of a ground state BPEA and fragmentation of the adduct radical results in the formation of reactive ammonium radical cation which is essentially responsible for the initiation.  相似文献   

7.
New systems for the visible‐light‐induced polymerization of cationic resins working through a free‐radical‐promoted process are presented. They are based on a photoinitiator (camphorquinone, isopropylthioxanthone, Eosin), a silane, and a diphenyl iodonium salt, the new compound being the silane. The overall efficiency is strongly affected by the silane structure. The rates of polymerization and final percent conversion are noticeably higher than those obtained in the presence of already studied reference systems. Moreover, contrary to previously investigated free‐radical‐promoted cationic polymerizations, oxygen does not inhibit the process and an unusual enhancement of the polymerization kinetics is found in aerated conditions: such an observation seems to have never been reported so far. The excited state processes and the role of oxygen as revealed by laser flash photolysis are discussed. The particular behavior of the silyl radicals is outlined. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2008–2014, 2008  相似文献   

8.
The spectral sensitivity of onium salt photoinitiators in cationic polymerization can be tuned from the short wavelength region of the UV spectrum to wavelengths up to the visible region by using direct and indirect activation, respectively. Indirect activation is based on the electron transfer reactions between onium salts and free radical photoinitiators, appropriate sensitizers and compounds capable of forming charge transfer complexes. Bisacylphosphine oxides, dimanganese decacarbonyl in conjunction with alkyl halides and titanocene type photoinitiators such as Irgacure 784 were shown to be useful free radical promoters providing the possibility of performing cationic polymerization in the long wavelength and visible region. The synthetic routes to prepare block copolymers by using electron transfer photosensitization and free radical promoted cationic polymerization are also described.  相似文献   

9.
A method is presented for the initiation of free‐radical and free‐radical‐promoted cationic photopolymerizations by in‐source lighting in the near‐infrared (NIR) region using upconverting glass (UCG). This approach utilizes laser irradiation of UCG at 975 nm in the presence of fluorescein (FL) and pentamethyldiethylene triamine (PMDETA). FL excited by light emitted from the UCG undergoes electron‐transfer reactions with PMDETA to form free radicals capable of initiating polymerization of methyl methacrylate. To execute the corresponding free‐radical‐promoted cationic polymerization of cyclohexene oxide, isobutyl vinyl ether, and N ‐vinyl carbazole, it was necessary to use FL, dimethyl aniline (DMA), and diphenyliodonium hexafluorophosphate as sensitizer, coinitiator, and oxidant, respectively. Iodonium ions promptly oxidize DMA radicals formed to the corresponding cations. Thus, cationic polymerization with efficiency comparable to the conventional irradiation source was achieved.  相似文献   

10.
The story of the discovery and development of onium salt photoinitiators for cationic polymerization is chronicled. The chemistry of the synthesis of these compounds is outlined, and the mechanisms of their initiation are discussed briefly. Among the most useful of these types of photoinitiators are diaryliodonium and triarylsulfonium salts, which are used widely for photoinduced cationic crosslinking reactions. From the very beginning, onium salt photoinitiated cationic polymerizations have found use in a multitude of practical applications. Specifically discussed in this article are the use of onium salts in coatings, adhesives, printing inks, release coatings, stereolithography, holographic recording, photocurable composites, and microelectronic photoresists. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4241–4254, 1999  相似文献   

11.
Pyridinium‐type salts containing an N‐ethoxy group belong to the family of onium salts and are photoinitiators appropriate for the polymerization of monomers such as oxiranes and vinyl ethers which are not polymerizable by a free radical mechanism. The initiation is accomplished by direct or indirect (sensitized) photolysis of the onium ion, with the former being restricted to the wavelength range of self absorption, the latter being applicable at wavelengths of visible light. An additionally useful tool, namely free radical‐mediated generation of initiating species enlarges the versatility of pyridinium salts as photoinitiators. In this connection, the oxidation of free radicals by pyridinium‐type ions and the free radical‐induced fragmentation of alkoxy pyridinium ions are addressed in this article. Moreover, an interesting application is noted concerning the synthesis of novel block copolymers with the aid of the onium salt‐based photopolymerization technique.  相似文献   

12.
Two novel redox initiator systems have been developed for carrying out the cationic polymerizations of vinyl and heterocyclic monomers. The initiators are based on various onium salts as the oxidant together with an alkylborane or an organosilane as the reducing agent. Using both redox cationic initiator systems, the polymerizations of a wide variety of monomers can be carried out at or below room temperature in the presence or absence of unreactive solvents. Also described in this communication is the novel use of a two-component redox system in which the reducing agent, a silane, is delivered to the monomer sample in the vapor state. Optical pyrometry (infrared thermography) was employed as a convenient method with which to monitor the polymerizations in real-time. A study of the effects of variations in the structures of the onium salt, the silane and the type of noble metal catalyst were carried out. The use of these initiator systems for carrying out commercially attractive crosslinking polymerizations for coatings, composites and electronic encapsulations is discussed.  相似文献   

13.
A new system for efficiently carrying out cationic photopolymerizations with visible and long‐wavelength UV light is described. This system is based on the principle that certain onium salt cationic photoinitiators can be reduced by free radicals produced by the hydrogen abstraction reactions of photoexcited ketones. Thus, when camphorquinone, benzil, 2‐isopropylthioxanthone, and 2‐ethylanthraquinone are irradiated in the presence of a monomer that can serve as a hydrogen donor, the resulting monomer‐bound radical rapidly reduces a diaryliodonium salt or a dialkylphenacylsulfonium salt, and the resulting monomer‐centered cations initiate the polymerizations of epoxides, vinyl ethers, and heterocyclic compounds. Onium salts with high reduction potentials, such as triarylsulfonium salts, do not undergo sensitization by this new system. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 343–356, 2001  相似文献   

14.
The chemistry and technology of photoinitiated cationic polymerization is a rapidly advancing field of investigation. This article reports on recent developments made in our laboratory in the development of new photoinitiators and photosensitizers. S,S-Dialkyl-S-phenacylsulfonium salts have been prepared using a new, highly efficient and cost-effective synthetic method and their use in the polymerization of various monomer systems studied. Also described is the development of alkoxyanthracene photosensitizers that may be employed to broaden the spectral sensitivity of various onium salt photoinitiators including the new S,S-dialkyl-S-phenacylsulfonium salts. A marked acceleration of the rate of the ring-opening polymerization of epoxide monomers was achieved using these photosensitizers. This article concludes with a brief discussion of the use of photoinitiated cationic polymerizations in such typical applications as can coatings, silicone release coatings and in stereolithography.  相似文献   

15.
Photosensitizers based on the carbazole structure were designed and developed for cationic polymerization. Along with triarylsulfonium and diaryliodonium salts, the carbazole derivatives showed a high photosensitization effect in the cationic photopolymerization of epoxides. The photophysical properties of the carbazole derivatives were studied in terms of electronic absorption, fluorescence, and phosphorescence spectrometry. Moreover, a unique photosensitization mechanism of the carbazole derivatives was discussed after studies of the fluorescence quenching, redox behavior, and kinetics of the photopolymerization by time‐resolved fluorescence spectrometry, cyclic voltammetry, and photo differential scanning calorimetry, respectively. The results confirmed the redox photosensitization of the carbazole derivatives in cationic polymerization. The photosensitization of the carbazole and its ring or N‐alkylated derivatives occurred predominantly in singlet excited states at the rate of the diffusion limit, whereas the carbazole derivatives with carbonyl substituents sensitized onium salts via triplet excited states on the basis of the Rehm–Weller equation in the photoinduced electron‐transfer process. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 90–100, 2000  相似文献   

16.
The development of iron complexes for the photoredox catalysis is a huge challenge. Indeed, Iron complexes can be ideal candidates due to their potential visible light absorption and redox properties but also because they are less toxic, inexpensive and environmentally friendly compared to other catalysts. In the present paper, a series of novel iron complexes have been synthesized and utilized to initiate the free radical promoted cationic polymerization of epoxides or the free radical polymerization of acrylates through photoredox catalysis processes upon exposure to near UV (385 nm) or visible violet (405 nm) light emitting diodes (LEDs). When combined with an iodonium salt and N‐vinylcarbazole, the iron complex‐based photoinitiating systems are able to generate radicals, cations, and radical cations. The initiation efficiency is investigated through real‐time Fourier transform infrared spectroscopy and a satisfactory initiating ability is found. The mechanisms for the generation of the reactive initiating species through photoredox catalysis are studied by different methods (steady state photolysis, cyclic voltammetry and electron spin resonance spin trapping techniques) and discussed in detail. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2247–2253  相似文献   

17.
Cationic photopolymerization of vinyl ethers by the sensitized photolysis of onium tetrakis(pentafluorophenyl)borate initiators has been investigated in this study. The onium borates were sensitized by anthracene and initiated the photopolymerization of the vinyl ethers. The rate of polymerization increased with the decrease in the free‐energy change from the excited singlet state of anthracene to the onium cation of the onium borates. The acid generated by the decomposition of the onium borates formed nonacidic products by heating. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 982–987, 2000  相似文献   

18.
The radiation-induced hybrid polymerization in the presence of the N-alkoxypyridinium salt having relatively stable nonnucleophilic anion (PF6) has been investigated in the paper. Based on the analysis of experimental data and the GPC spectrum, the onium salts not only oxidize -alkoxyalkyl radicals, produced from IBVE in dichloromethane by irradiation, to the corresponding cations, but also give nonnucleophilic anions PF6 for the polymerization system. The experimental results clearly demonstrate that free radical and cationic polymerization mechanisms occurred simultaneously in IBVE/EMP+PF6/CH2Cl2 systems on irradiation with γ-ray.  相似文献   

19.
Four novel onium salts (onium‐polyoxometalate) have been synthesized and characterized. They contain a diphenyliodonium or a thianthrenium (TH) moiety and a polyoxomolybdate or a polyoxotungstate as new counter anions. Outstandingly, these counter anions are photochemically active and can sensitize the decomposition of the iodonium or TH moiety through an intramolecular electron transfer. The phenyl radicals generated upon UV light irradiation (Xe–Hg lamp) are very efficient to initiate the radical polymerization of acrylates. Cations are also generated for the cationic polymerization of epoxides. Remarkably, these novel iodonium and TH salts are characterized by a higher reactivity compared with that of the diphenyliodonium hexafluorophosphate and the commercial TH salt, respectively. Interpenetrating polymer networks can also be obtained under air through a concomitant cationic/radical photopolymerization of an epoxy/acrylate blend (monomer conversions > 65%). The photochemical mechanisms are studied by steady‐state photolysis, cyclic voltammetry, and electron spin resonance techniques. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 981–989  相似文献   

20.
An investigation of the excited state processes in a three-component initiating system based on a new ketone/amine/onium salt combination has been carried out for the first time. The results obtained through time-resolved laser spectroscopy and the data gained in radical photopolymerization experiments suggest that the addition of an onium salt to the usual ketone/amine system mostly result in a decrease of the termination reaction of the growing macromolecular chains, thus allowing an increase of the rate of polymerization. © 1993 John Wiley & Sons, Inc.  相似文献   

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