Polymerization photopolymerization

Radiation-induced polymerization (photopolymerization) is an efficient method for fast generation of highly crosslinked polymer networks from liquid resin systems. 

A key concept in photochemistry is that of the quantum yield for process n, , defined as in Eq. 16.6. For example, the fluorescence quantum yield, f, is equal to the number of photons emitted divided by the number of photons absorbed. If all possible processes are considered, then the sum of all quantum yields should be 1.0 in typical systems. A formal exception to this rule is the case of a photochemically initiated polymerization, photopolymerization. In this case, if we define the quantum yield as the number of couplings between monomers divided by the number of photons absorbed, we expect to see d> > > 1. 

The earliest reported polymerization of vinyl fluoride involved heating a saturated solution of VF in toluene at 67°C at 600 MPa for a period of 16 hours. In another study, benzoyl peroxide was the polymerization initiator. A polymer was produced with a density of 1.39 g/cm which could be dissolved in hot dimethylformamide, chlorobenzene, and other polar solvents. A great many initiators and vinyl fluoride polymerization conditions have been studied. Examples ofbulk f ] and solution[ ][ F[i04] pp lymerizations have been reported. Aqueous suspension or emulsion techniques have been generally preferable over other methods.Vinyl fluoride volatility required the use of moderately high pressures during the polymerization. Photopolymerization of VF, aided by a free-radical initiator, has also been accom-... 

M TS 00 iS V oo 3 Crosslinking during polymerization Free radical polymerization Theimal polymerization Photopolymerization Radiation polymerization Plasma polymerization Copolymerization between various divinyl monomers and divinyl compounds... 

Chemical hydrogels are 3D crosslinked networks that formed by new covalent bonds between water-soluble macromers. To use chemical hydrogels for biomedical application, chemical reactions should not damage incorporated biopharmaceuticals or cells. There are several chemical crossUnking methods such as redox-initiated polymerization, photopolymerization, classical organic reactions between functional groups, and enzymatic reactions. 

Photopolymerization reactions of monolayers have become of interest (note Chapter XV). Lando and co-workers have studied the UV polymerization of 16-heptadecenoic acid [311] and vinyl stearate [312] monolayers. Particularly interesting is the UV polymerization of long-chain diacetylenes. As illustrated in Fig. IV-30, a zipperlike process can occur if the molecular orientation in the film is just right (e.g., polymerization does not occur readily in the neat liquid) (see Refs. 313-315). 

An alternative approach envisages the stimulating idea to produce an all-carbon fullerene polymer in which adjacent fullerenes are linked by covalent bonds and align in well characterized one-, two- and tliree-dimensional arrays. Polymerization of [60]fullerene, with the selective fonnation of covalent bonds, occurs upon treatment under pressure and relatively high temperatures, or upon photopolymerization in the absence of a triplet quencher,... 

Dry-Film Resists Based on Radical Photopolymerization. Photoinitiated polymerization (PIP) is widely practiced ia bulk systems, but special measures must be taken to apply the chemistry ia Hthographic appHcations. The attractive aspect of PIP is that each initiator species produced by photolysis launches a cascade of chemical events, effectively forming multiple chemical bonds for each photon absorbed. The gain that results constitutes a form of "chemical amplification" analogous to that observed ia silver hahde photography, and illustrates a path for achieving very high photosensitivities. 

Photopolymerization and Plasma Polymerization. The use of ultraviolet light alone (14) as well as the use of electrically excited plasmas or glow discharges to generate monomers capable of undergoing VDP have been explored. The products of these two processes, called plasma polymers, continue to receive considerable scientific attention. Interest in these approaches is enhanced by the fact that the feedstock material from which the monomer capable of VDP is generated is often inexpensive and readily available. In spite of these widespread scientific efforts, however, commercial use of the technologies is quite limited. 

Vlayl fluoride undergoes free-radical polymerization. The first polymerization iavolved heating a saturated solutioa of VF ia tolueae at 67°C uader 600 MPa (87,000 psi) for 16 h (24). A wide variety of ioitiators and polymerization conditions have been explored (25—27). Examples of bulk (28,29) and solution (25,28,30,31) polymerizations exist however, aqueous suspension or emulsion methods are generally preferred (26,32—40). VF volatiflty dictates that moderately high pressures be used. Photopolymerizations, usually incorporating free-radical initiators, are also known (26,28,29,35). 

Polymers are only marginally important in main memories of semiconductor technology, except for polymeric resist films used for chip production. For optical mass memories, however, they are important or even indispensable, being used as substrate material (in WORM, EOD) or for both substrate material and the memory layer (in CD-ROM). Peripheral uses of polymers in the manufacturing process of optical storage media are, eg, as binder for dye-in-polymer layers or as surfacing layers, protective overcoatings, uv-resist films, photopolymerization lacquers for repHcation, etc. 

Photopolymerization. In many cases polymerization is initiated by ittadiation of a sensitizer with ultraviolet or visible light. The excited state of the sensitizer may dissociate directiy to form active free radicals, or it may first undergo a bimoleculat electron-transfer reaction, the products of which initiate polymerization (14). TriphenylaLkylborate salts of polymethines such as (23) ate photoinitiators of free-radical polymerization. The sensitivity of these salts throughout the entire visible spectral region is the result of an intra-ion pair electron-transfer reaction (101). 

Photopolymerization reactions are widely used for printing and photoresist appHcations (55). Spectral sensitization of cationic polymerization has utilized electron transfer from heteroaromatics, ketones, or dyes to initiators like iodonium or sulfonium salts (60). However, sensitized free-radical polymerization has been the main technology of choice (55). Spectral sensitizers over the wavelength region 300—700 nm are effective. AcryUc monomer polymerization, for example, is sensitized by xanthene, thiazine, acridine, cyanine, and merocyanine dyes. The required free-radical formation via these dyes may be achieved by hydrogen atom-transfer, electron-transfer, or exciplex formation with other initiator components of the photopolymer system. 

This result reveals that exciplex formation plays a principal role in the initiation of polymerization. Since the absorption band is broadened toward longer wavelengths as the result of formation of CTC between AN and aniline, a certain concentration of aniline can be chosen so that 365-nm light is absorbed only by the CTC but not by the aniline molecule. Therefore, in this case the photopolymerization may be ascribed to the CTC excitation selected. For example, a 5 x 10 mol/L aniline solution in AN could absorb light of 365 nm, while solutions in DMF or cyclohexane with the same concentration will show no absorption. Obviously, in this case the polymerization of AN is caused by CTC excitation. The rates of polymerization for different amines were found to be in the following order (Table 12) ... 

Li et al. [87,88] found that aniline will process the photopolymerization of AN either in N,N-dimethylformamide (DMF) solution or in bulk with a fair rate of polymerization only next to DMT. From UV spectra it is proved that aniline will form a CTC with AN. Using 313-nm radiation that CTC is excited to an exciplex and polymerization proceeds. N-methylaniline will polymerize AN similarly. The following mechanism was proposed ... 

The well-known photopolymerization of acrylic monomers usually involves a charge transfer system with carbonyl compound as an acceptor and aliphatic tertiary amine, triethylamine (TEA), as a donor. Instead of tertiary amine such as TEA or DMT, Li et al. [89] investigated the photopolymerization of AN in the presence of benzophenone (BP) and aniline (A) or N-methylaniline (NMA) and found that the BP-A or BP-NMA system will give a higher rate of polymerization than that of the well-known system BP-TEA. Still, we know that secondary aromatic amine would be deprotonated of the H-atom mostly on the N-atom so we proposed the mechanism as follows ... 

We have prepared a copolymer-bearing amino side group and used it either alone or in combination with BP to initiate the photopolymerization of MM A [89]. The gel permeation chromatography (GPC) plot of PMMA initiated by the former system showed a bimodal distribution of molecular weight because both the radicals produced initiate polymerization as follows ... 

The polymers initiated by BP amines were found to contain about one amino end group per molecular chain. It is reasonable to consider that the combination of BP and such polymers will initiate further polymerization of vinyl monomers. We investigated the photopolymerization of MMA with BP-PMMA bearing an anilino end group as the initiation system and found an increase of the molecular weight from GPC and viscometrical measurement [91]. This system can also initiate the photopolymerization of AN to form a block copolymer, which was characterized by GPC, elemental analysis, and IR spectra. The mechanism proposed is as follows ... 

Photopolymerization, in general, can be defined as the process whereby light is used to induce the conversion of monomer molecules to a polymer chain. One can distinguish between true photopolymerization and photoinitiation of polymerization processes. In the former, each chain propagation step involves a photochemical process [1,2] (i.e., photochemical chain lengthening process in which the absorption of light is indispensable for... 

Photopolymerization of MMA was also carried out in the presence of visible light (440 nm) using /3-PCPY as the photoinitiator at 30°C [20]. The initiator and monomer exponent values were calculated as 0.5 and 1.0, respectively, showing ideal kinetics. An average value of kp /kt was 4.07 x 10 L-mol -s . Kinetic data and ESR studies indicated that the overall polymerization takes place by a radical mechanism via triplet carbene formation, which acts as the sources of the initiating radical. 

Previously, the same author [52] reported that compounds containing the tricoordinated sulfur cation, such as the triphenylsulfonium salt, worked as effective initiators in the free radical polymerization of MMA and styrene [52]. Because of the structural similarity of sulfonium salt and ylide, diphenyloxosulfonium bis-(me-thoxycarbonyl) methylide (POSY) (Scheme 28), which contains a tetracoordinated sulfur cation, was used as a photoinitiator by Kondo et al. [63] for the polymerization of MMA and styrene. The photopolymerization was carried out with a high-pressure mercury lamp the orders of reaction with respect to [POSY] and [MMA] were 0.5 and 1.0, respectively, as expected for radical polymerization. 

HPO group is sensitive to light, but stable to heat. Using this MAI, St was thermally polymerized at the first step, and then MMA was photopolymerized at the second step [12]. Block efficiency was 40-55% and the amount of PSt homopolymer decreased, while that of PMMA homopolymer increased, presumably due to chain transfer reaction. 

As an example stereolithography is a 3-D rapid process that produces automatically simple to very complex shaped models in plastic. Basically it is a method of building successive layers across sections of pho-topolymerized plastics on top of each other until all the thin printed layers can be joined together to form a whole product. The chemical key to the process, photopolymerization, is a well established technology in which a photo initiator absorbs UV energy to form free radicals that then initiate the polymerization of the liquid monomers. The degree... 

While the products of 2-furaldehyde polymerization by heat are branched polycondensates with highly conjugated structures (see Section Il-C), the photopolymerization of this furan derivative gives a linear polyaddition product 24>7S). 

Dithiocarbamatc 16 has been used to prepare low dispersity PMAA ( Mw 1 Mn-1.2).52 Photopolymerization of S in the presence of dithiocarbamate 16 also displays some living characteristics (molecular weights that increase with conversion, ability to make block copolymer). However, 17 appears to behave as a conventional initiator in S polymerization.53 The difference in behavior was attributed to the relatively poor leaving group ability of the 2-carboxyprop-2-yI radical. This hypothesis is supported by MO calculations. Dithiocarbamatc 17 was used to control polymerizations of MMA,54 HEMA54 and NIPAM.5... 

The Lewis acid is important for polymerization. Surprisingly, the present author did not find evidence for or against the aryl cation (Ar+) as a polymerization initiator. Green and Stark (1981) briefly reviewed the photopolymerization of epoxides. 

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