Vinyl cinnamate

Poly(vinyl cinnamate) Resists. Dichromated resists exhibit numerous shortcomings which include lot-to-lot variabiUty of the components, aging of the formulated resists in solution and in coated form, poor process stabiUty (due to a sensitivity to variations in temperature and humidity), and intrinsically low photosensitivity requiring long exposure times for adequate insolubilization. 

Fig. 4. Chemistry of poly(vinyl cinnamate) negative-acting resist. Initial light absorption by the photosensitizer is followed by energy transfer to produce a pendant cinnamate group in a triplet electronic state. This combines with a second cinnamate on another polymer chain, forming a polymer—polymer...

Poly(vinyl cinnamate) is not used in the traditional areas of plastics technology but its ability to cross-link on exposure to light has led to important applications in photography, lithography and related fields as a photoresist. 

As with poly(vinyl alcohol), poly(vinyl cinnamate) is prepared by chemical modification of another polymer rather than from monomer . One process is to treat poly(vinyl alcohol) with cinnamoyl chloride and pyridine but this is rather slow. Use of the Schotten Baumann reaction will, however, allow esterification to proceed at a reasonable rate. In one example poly(vinyl alcohol) of degree of polymerisation 1400 and degree of saponification of 95% was dissolved in water. To this was added a concentrated potassium hydroxide solution and then cinnamoyl chloride in methyl ethyl ketone. The product was, in effect a vinyl alcohol-vinyl cinnamate copolymer Figure 14.8)... 

Figure 1 Left illustration of the application of a mask to produce different samples . Right FT-IR images of the carbonyl band of poly(vinyl cinnamate), showing different levels of crosslink density as revealed from a decrease in conjugated carbonyls. Reproduced from Rafferty et al. [9], Copyright 2002, with permission from the Society for Applied Spectroscopy.

Photocrosslinking. The second class of photopolymer chemistry that is used in some commercial products is based on the reaction of unsaturated moieties attached to an organic polymer. These photopolymer materials include the [2+2] cycloaddition of the ethylenic groups in poly(vinyl cinnamate) polymers and in the newer styryl pyridinium (10) and thiazolium (77) derivatives of poly(vinyl alcohol). The main advantage of this chemistry is that, unlike free-radical photopolymerization, they are insensitive to the presence of oxygen. This photopolymer mechanism is principally used in applications employing a washout development process (e.g. resists). 

A successful example of sensitization is found in the case of poly(vinyl cinnamate) (7). 

Photo-crosslinking and the reverse process of photodissociation of pre-existing crosslinks relies on a cycloaddition reaction (and on the reverse dissociation of the cyclic adduct). For example, derivatives of vinyl cinnamic acid can form crosslinks which are dissociated by irradiation with short wavelength light (e.g. 254 nm produced by low-pressure mercury arcs). In this process the polymer chains become separated, and the polymer itself is then soluble in organic solvents. 

Typical photosensitizer (PS) Poly(vinyl cinnamate) (PVCn)... 

Cinnamates occupy an important place in the history of photochemistry. Schmidt and his co-workers [18] used the solid state photochemistry of cinnamic acid and its derivatives to develop the idea of topochemical control of photochemistry in the crystalline state. Minsk [19] developed poly(vinyl cinnamate) as the first polymer for photoimaging. The cinnamate chromophore is still commonly incorporated in photopolymers of all types, including LC polymers, to enable them to be photochemically cross-linked [20], and a number of reports of the photochemistry of such MCLC and SCLC polymers are summarized below. 

TABLE I, . Synthesis and caracteristies of 4-vinyl cinnamic derivatives. ... 

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