Photosensitive monomers

The cured polymer samples used for physical property testing were prepared by photocuring 12 mil thick sheets of degassed and photosensitized monomer mixtures, using a mold composed of glass plates lined with polyester film and separated by a double thickness of vinyl electrical tape. A GE sunlamp was used for Illumination, and Darocure 1173 (E. Merck) was used as the photoinitiator. Hydrocarbon monomers were used as received from the manufacturers. All the vinyl group-containing compounds were stored at -5°C until use. 

Accordingly, the synthesis of novel cinnamate polymers with high functionality and performance is very important from the viewpoint of both polymer chemistry and practical use. Recently, we have reported the synthesis of polymers with pendant photosensitive moieties such as cinnamic ester and suitable photosensitizer groups by radical copolymerizations of 2-(cinnamoyloxy) ethyl methacrylate with photosensitizer monomers (9), by copolymerizations of chloromethylated styrene with the photosensitizer monomers followed by the reactions of the copolymers with salts of... 

Typical Procedure for Cationic Copolymerization of CEVE with Photosensitizer Monomer. CEVE (9.81 g 45 mmol) and 0.86 g (5 mmol) of NPVE were dissolved in 50 ml of toluene and the solution cooled with dry ice/methanol. Next 0.13 ml (1 mmol) of TFB was dissolved in 5 ml of toluene... 

Syntheses of Self-Sensitized Polymers by Cationic Copolymerizations. The cationic polymerizations of several vinyl ethers containing pendant ester groups such as cinnamic ester 12), methacrylic ester 16), acrylic ester (77), and crotonic ester 18) have been reported. Based on these reports, cationic copolymerizations of CEVE with photosensitizer monomers such as NPVE, NNVE, VNP and NPEVE were carried out using TFB as a catalyst in toluene at — 65 °C. Each copolymer was obtained with high yield except in the case of copolymerization of CEVE with VNP as summarized in Table I. 

The cationic copolymerizations of CEVE M ) with NPVE M2) and NNVE (M2) gave the copolymers with the photosensitizer monomer in proportion to the photosensitizer monomers in the charge when the molar content of M2 was lower than 30 mol-%. However, copolymers with equal amounts of photosensitizer units were not obtained by the copolymerization of 60 or 70 mol-% of CEVE with 40 mol-% of NPVE and 30 mol-% of NNVE in toluene, because a portion of the photosensitizer monomer in each case was precipitated during the copolymerization under similar reaction conditions. 

Syntheses of Polymeric Photosensitizers and Self-sensitized Polymers by the Reactions of PCVE. Photosensitizer monomers such as NPVE, NNVE and NPEVE were synthesized by the reaction of excess CVE with potassium salts of the corresponding photosensitizing compounds using TBAB as a phase transfer catalyst as described in the experimental part. Substitution reactions of chloroethyl groups in PCVE with PNP and PNN were also carried out using TBAB as a phase transfer catalyst in DMF at 80 C for 24 h. 

Self-supported photoresponsive MIP membranes synthesised using a photosensitive monomer, p-phenylazo-acrylanilide, and dansylamine as template, have been applied as recognition element in sensors [207, 208]. The binding capacity of the membrane for dansylamide could be reversibly modified by changing the illumination of membrane. Other examples are NADH and NADPH imprinted membranes... 

Curing by light irradiation can be apphed to a variety of polymers. The acrylic family is a typical example of photosensitive monomers. A well-documented review has recently been dedicated to the curing of composites by ultraviolet radiation [45], Photocuring time is much shorter than for traditional thermal curing (minutes rather than hours), leading to a significant reduction in the cycle time. 

The copolymerization of photosensitive monomers with conventional comonomers enables synthesis of polymeric systems bearing the photoreactive moieties at different distance from each other, thus allowing modulation of their initiation activity for specific applications. 

Interesting properties can be engineered into these materials by copolymerization. Copolymerization of 2-ethylacrylic acid or MAA with iV-[4-(phe-nylazo)phenyl]methacrylamide, a photosensitive monomer, results in polymers in which the interaction with lipid biolayers can be photoregulated [10, 11]. Thermally reversible polymers can be produced from poly(iV-isopropylacryla-mide), which is a water-soluble polymer at room temperature. The LCST (lower critical solution temperature) of the homopolymer is 32 °C at this temperature a reversible phase separation occurs. This LCST can be adjusted by copolymerization with more or less hydrophilic monomers. 

In resists of this class, the imaging layer contains a multifunctional monomer that can form an intercormected network upon polymerization, and a photosensitizer to generate a flux of initiating free radicals. Although not stricdy required for imaging, the composition usually includes a polymeric binder (typically an acryhc copolymer) to modify the layer s physical properties. Figure 7b shows the chemical stmctures of typical components. 

If (P ) is terminated by a chain transfer to a solvent or a monomer, a graft copolymer is formed, or, if the termination is from a combination, a crosslinked network polymer is formed. If the pre-existing polymer (B) contains an end group that itself is photosensitive (or can produce a radical by interacting with photoinitiator) and in the presence of a vinyl monomer (A), block copolymer of type AB can be produced if the photosensitive group is on one end of the polymeric chain. Type ABA block copolymer can be produced if the polymer chain (B) contains a photosensitive group on both ends. 

Studies in the photoinitiation of polymerization by transition metal chelates probably stem from the original observations of Bamford and Ferrar [33]. These workers have shown that Mn(III) tris-(acety]acetonate) (Mn(a-cac)3) and Mn (III) tris-(l,l,l-trifluoroacetyl acetonate) (Mn(facac)3) can photosensitize the free radical polymerization of MMA and styrene (in bulk and in solution) when irradiated with light of A = 365 at 25°C and also abstract hydrogen atom from hydrocarbon solvents in the absence of monomer. The initiation of polymerization is not dependant on the nature of the monomer and the rate of photodecomposition of Mn(acac)3 exceeds the rate of initiation and the initiation species is the acac radical. The mechanism shown in Scheme (14) is proposed according to the kinetics and spectral observations ... 

Photo-induced grafting onto wood cellulose with several vinyl monomers using phenyl acetophenone and benzophenone derivatives as photosensitizers has been reported [72]. A fast increase in grafting was observed for short irradiation times, whereas longer ones resulted in a decreased percent grafting. 

The reaction between Cell—O radical and vinyl monomers leads to the formation of grafted cellulose. In the presence of photosensitizers generally used as photoinitiators, such as benzophenone and phenylace-tophenone derivatives, the photoinitiator absorbs the UV radiation and transforms to its singlet (S ) and then triplet (T ) states. After that it may decompose into free radicals or transfer its energy to cellulose or any other molecules in the system. Take benzophenone as an example ... 

Clearly, unless monomer is the intended photoinitiator, it is important to choose an initiator that absorbs in a region of the UV-visible spectrum clear from the absorptions of monomer and other components of the polymerization medium. Ideally, one should choose a monochromatic light source that, is specific for the chromophorc of the photoinitiator or photosensitizer. It is also important in many experiments that the total amount of light absorbed by the sample is small. Otherwise the rate of initiation will vary with the depth of light penetration into the sample. 

The ordinary monomer units of PVC are not expected to absorb any terrestrial solar radiation (1>.2>.3 A) Thus, under the usual ambient conditions, photodegradation of the polymer must be initiated by chromophoric impurities. These impurities may simply be structural defects in the PVC itself, or they may be extraneous substances that have been incorporated into the polymer. Several of these potential photosensitizers are discussed in the following sections. 

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