Poly-4-vinylphenol

In the development of a reactive non-chrome post-treatment, a variety of phenolic resins were synthesized and commercial phenolic resins evaluated. It was found that phenol-formaldehyde resins, creso1-forma1dehyd e condensates, ortho-novo 1 ak resins, and phenol-formaldehyde emulsions gave positive results when employed as post-treatments over zinc and iron phosphate conversion coatings. The above materials all possessed drawbacks. The materials in general have poor water solubility at low concentrations used in post-treatment applications and had to be dried and baked in place in order to obtain good performance. The best results were obtained with poly-4-vinylphenol and derivatives thereof as shown in the following structure (8,9,10)... 

The "Mannich" adduct synthesized from the condensation of formaldehyde, 2-(methylamino)ethanol and poly-4-vinylphenol as shown in Structure I, has been evaluated as a function of molecular weight versus corrosion resistance as measured by salt spray and humidity tests on Bonderite 1000, an iron phosphate conversion coating. The molecular weight of the polymer was varied from approximately = 2,900 to 60,000. The corrosion resistance results were essentially equivalent over the molecular weight range evaluated. 

On zinc phosphate conversion coatings, the "Mannich" derivatives of poly-4-vinylphenol have demonstrated performance equivalent to chromic chromate systems in salt spray, humidity, and physical testing. In addition. Table III illustrates results observed with automotive body paint systems evaluated by the "scab" or "cycle" test which causes failure more typical of actual end use conditions than do salt spray evaluations. Again, results equivalent to chromic-chromate post-treatments were obtained. In addition, the humidity resistance and adhesion tests were essentially equivalent to the chromium controls. 

Kriz J, Dybal J, Brus J. Cooperative hydrogen bonds of macromolecules. 2. Two-dimensional cooperativity in the binding of poly(4-vinylpyridine) to poly(4-vinylphenol). J Phys Chem B 2006 110 18338-18346. 

A modification of these systems involving replacement of poly (4-vinylphenol) with poly(methyl isopropenyl ketone) (PMIPK) was reported by Nakane and co-workers (41). Although PMIPK is a positive-acting singlecomponent resist in the deep UV, it functions as a negative resist when mixed with an aromatic bisazide such as 2,6 di(4-azidobenzylidene)-4-... 

Fig. 6.5. Thermally initiated cross-linking reaction of poly-4-vinylphenol with poly(melamine-co-formaldehyde) methylated as a cross linking agent.

Af,Af-Dimethylaminopyridine, triethylamine, CH2CI2, phthalic anhydride Poly(4-vinylphenol), 4-(dimethylamino)-pyridinium 4-toluenesulfonate (0.786 mmol), THF, CH2CI2,4-(trifluorovinyloxy) benzoyl chloride, di-isopropylethyl-amine, 1,2-dicyclohexyl-carbodiimide... 

Vacuum dried poly(4-vinylphenol) (0.9436 g), 4-(dimethylamino)pyridinium 4-to-luenesulfonate (0.786 mmol), and the Step 11 product (1.044g) were dissolved into 30 ml of THF and 10 ml of CH2CI2. After the addition of 1,2-dicyclohexylcarbodii-mide (1.965 mmol) the solution was stirred at ambient temperature for 40 hours. Thereafter 4-(trifluorovinyloxy) benzoyl chloride (17.12 mmol), 1,2-dicyclohexyl-carbodiimide, and di-isopropylethylamine (14 mmol) were added, and the mixture stirred an additional 24 hours. The solution was then concentrated to about 10 ml and precipitated in methanol. The solid was isolated, re-dissolved in CH2CI2, and reprecipitated in methanol, the process being repeated 10 times. The product was dried and 2.43 g were isolated as a dark blue powder. 

For example, placing a base-sensitive polymer, poly(4-vinylphenol), under the water-containing poly(2-hydroxyethyl methacrylate) produces a response for pH in a water solution over the laminate. However, if the water containing polymer is... 

Examples of homopolymers are given. Poly(4-vinylphenol) was prepared as a prepolymer for the subsequent alkylation [55]. Poly[2-(4-vinylbenzyl)hydroqui-none] 65 is an example of the unhindered phenolic antioxidant for rubbers. Many homopolymers bear a hindered phenolic moiety. Homopolymer 66 was proposed for blending with BR and IR [56]. Other examples are poly[vinyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] [57] (67), poly(3,5-di-/ert-butyl-4-hydroxy-benzyl methacrylate) [58] (68) or poly[iV-3,5-di-tert-butyl-4-hydroxybenzyl) male-imide] [59] (69). Numerous polymeric antioxidants are functionalized with aromatic amine groups. Poly(4-anilinophenyi methacrylate) [53] (70) serves as an example. 

Chlorinated, sulfonated, chlorosulfonated or epoxidized polymers, homopolymers and copolymers of functionalized monomers, e.g. poly(methacryl aldehyde), poly(2,3-epoxypropyl acrylate), poly(4-vinylphenol), poly(propylene-co-10-unde-cene-l-ol), poly(butadiene-co-methacryl aldehyde), poly(butadiene-co-acrylic acid), poly(ethylene-co-alkyl acrylate), poly(alkyl acrylate-co-2,3-epoxypropyl acrylate), poly(alkyl acrylate-co-maleic anhydride), poly(styrene-co-4-vinylbenzyl chloride)... 

Friedel-Crafts alkylation was used for introduction of tert-butyl groups into poly(4-vinylphenol) [55]. 

One polymer from this class that has been studied by Py-GC/MS is poly(4-vinylphenol) or poly(4-hydroxystyrene), CAS 24979-70-2, with the idealized structure -[CH2CH(p-C6H40H)-]n. The results are shown in Figure 6.6.1. The pyrolysis was done similarly to other polymers previously discussed in this book at 600° C in He with the separation on a Carbowax column (see Table 4.2.2) and with MS detection. The peak identification for the chromatogram was done using MS spectral library searches and is given in Table 6.6.2. 

Poly(4-vinylphenol) gives by pyrolysis a proportion of monomer lower than polystyrene. The dimer, if formed from the pyrolysis, is not seen in the pyrogram since the chromatographic conditions are not appropriate for its elution. However, the pyrolysis mechanism for poly(4-vinylphenol) is very likely similar to that of polystyrene. 

Off-line pyrolysis of a poly(4-vinylphenol) sample followed by the silylation using N,0-bis(trimethylsilyl)-trifluoroacetamide (BSTFA) of the pyrolysate and GC/MS analysis with separation on a DB5 column (30 m length. 0.32 mm i d., 0.32 pm film thickness) is shown in Figure 6.6.2. The identification of the compounds in the silylated pyrolysate was done using MS library searches and is given in Table 6.6.3... 

Figure 6.6.2. Result fora off-line pyrolysis of a poly(4-vinylphenol) M = 8000 followed by silylation and GC/MS analysis. Pyrolysis done at BOCP C in He, with the separation on a 5% phenyl methylsilicone column.

The miscibility of poly(4-vinylpyridine) (P4VP) with poly(4-vinylphenol) (PVPh) blends was investigated over a wide range of compositions by other techniques and high-resolution solid-state NMR. ° Relaxation times were studied as a function of blend composition. Ti(H) and Tip(H) results demonstrate that the spin diffusion can completely average out the entire relaxation process. It was also found that the intimate mixing of the polymer blends restricts the local chain mobility. 

P3AT (poly(3-alkylthiophene)) 76, 317 P4VP (poly(4-vinylphenol)) 518, 519, 530 PAHs (polycyclic aromatic hydrocarbons) 62... 

Another example from polymer blends can be taken from the dynamics of the faster poly(ethyl methacrylate) (PEMA, Tg = lA C) component in blends with poly(4-vinylphenol) (PVPh, Tg = 171 C) (Zhang et al 2002). Neat PEMA has a resolved JG relaxation, which is continued to be observed in the blend and practically unchanged with blending. Since Tg of the PEMA component in the blend is shifted to higher temperature by the slower poly(4-vinylphenol) component, therefore ogXaf Tgf) - ogxpf Tgf)) of the PEMA component increase at constant Xa(Tg). 

Wang, J., Cheung, M. K., and Mi, Y. 2001. Miscibility of poly(ethyl oxazoline)/ poly(4-vinylphenol) blends as investigated by the high-resolution solid-state 13C NMR. Polymer 42 2077-2083. 

Pfefferkom et al., 2011), poly (iso-butyl methaciylate) (PiBMA) (Katime and Cadenato, 1995), poly(tert-butyl methaciylate) (PtBMA) (Katime and Cadenato, 1995), and poly(4-vinylphenol-co-2-hydroxyethyl methaciylate) (PVPh-HEM) (Pereira and Rocco, 2005) are found to be miscible with PEO. Owing to the vast differences both in the surface stractuie and T s of PEO and PMMA (T s for PEO... 

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