Poly chloromethyl substituted

T. Nishikubo, T. lizawa, K. Kobayashi, and M. Okawara, Substitution reaction of poly(chloromethyl-... 

Modifications of chloromethyl substituted polystyrene and poly(vinyl halides). 

Chloromethyl substituted polystyrenes can also be prepared from poly(p-methyl styrene)s by treating them with aqueous sodium hypochlorite in the presence of a phase transfer catalysts, like benzyltriethylammonium chloride. The conversions of methyl to chloromethyl groups can be as high as 20% without any detectable formation of dichloromethyl groups. When, however, the reactions are pushed to conversions as high as 61%, some dichloromethyl groups form. 

Due to its ready availability, high reactivity and other interesting properties, chloromethyl substituted polystyrene (I) has been the most extensively studied substrate in chemical modification via phase transfer catalysis. Reactions have been carried out both on soluble poly(chloromethyl styrene) (Ref. 12,... 

An important side reaction is the formation of diaryl methane derivatives ArCHaAr. Moreover poly substituted products may be obtained as minor products. Aromatic compounds have been treated with formaldehyde and hydrogen bromide or hydrogen iodide instead of hydrogen chloride. The formaldehyde may be replaced by another aldehyde the term Blanc reaction however stands for the chloromethylation only. 

For poly silanes made by Wurtz reaction, the presence of functional groups in polysilane polymers is limited by the vigorous conditions of the sodium condensation reaction. Any substituents that react with molten sodium metal must therefore be introduced after the polymer is synthesized. Halogen atoms can be introduced into alkenylpolysilanes by HBr or HC1 addition reactions, as shown for the 3-cyclohexenyl-ethyl polymers in equation (21).37 Chlorine atoms have also been introduced into arylpolysilanes by chloromethylation, in which -CH2C1 groups are substituted onto phenyl rings in the polymer.38... 

Chloromethylated polystyrene and chloromethylated poly(a-methyIstyrene) are negative type resists having high sensitivity and high resolution. In the pulse radiolysis of solid films of this polymer, the absorption spectra of substituted benzyl-type polymer-radical and the charge transfer complex between phenyl rings and chlorine atoms were observed (Fig. 17) [59], The benzyl-type radical may be produced by the dissociative electron attachment to the benzyl part of chloromethylated polystyrene (CMS). 

Polysiloxanes. The initial reports of the utility of polysiloxanes for lithographic applications spurred several research groups to further investigate this class of materials. The problem of low Tg was addressed by preparing chloromethylated poly(diphenylsiloxane) 16, 17). More recently, poly(sil-sesquioxanes) 18, 19) have been reported as sensitive, negative, e-beam, ion-beam, and UV resists. These soluble, ladder -type polymers prepared by the hydrolysis of substituted chloro- and alkoxysilanes are high-Tg materials (150 °C) with high silicon contents. 

The relationship between structure and photoinitiation activity has been examined for polymeric systems bearing side-chain 1-substituted cyclohexyl-phenyl ketone moieties in the UV curing of the HDDA/BA equimolar mixture [19,20]. Indeed, the activity of poly[(l-acryloxycyclohexyl)phenyl ketone] [poly (APK)] and styrene/4-chloromethyl-styrene/l-(4-styrylmethyloxy)cyclohexyl phenyl ketone copolymers (PABOK) has been compared with that of the corresponding low-molecular-weight structural models such as 1-hydroxy-cyclohexyl phenyl ketone (HPK), 1-acetoxy-cyclohexyl phenyl ketone (ACPK) and l-(4-isopropyl-benzyloxy) cyclohexyl phenyl ketone (PIBOK). 

The pyrogram of poly(vinyl benzyl chloride) is very simiiar to that of other polystyrene related polymers. The presence of two main monomer peaks in the pyrogram is caused by the fact that the polymer is a mixture of 3 and 4 substituted polymer. The peak area ratios of several 3- and 4-isomers is around 60/40. For example, for 1-(chloromethyl)-3-methylbenzene and 1-(chloromethyl)-4-methylbenzene the ratio is 59.9/40.1, for 1-(chloromethyl)-3-ethylbenzene and 1 -(chloromethyl)-4-ethylbenzene the ratio is... 

The contribution to Ndc of the Cl atom in poly(vinyl chloride), where a backbone carbon atom is asymmetrically substituted by a Cl atom, is 8. The contribution to Ndc of the two Cl atoms symmetrically substituted to the same backbone carbon atom in poly(vinylidene chloride) is zero. Since the two Cl atoms are not attached to the backbone atom but located on pendant chloromethyl groups, the contribution of Cl atoms in poly(oxy-2,2-dichloromethyltrimethylene) is 16 despite the fact that the backbone carbon atom is symmetrically substituted. 

When the Cu(II) complex of cyclen (AE) was attached to cross-linked polystyrene, the proteolytic activity of the Cu(II) complex of cyclen was enhanced remarkably (111). Poly(chloromethylstyrene-co-divinylbenzene) (PCD) was prepared as a derivative of polystyrene in which all of the styryl residues contained chloromethyl groups. By the substitution of chloro groups of PCD with various nucleophiles, PCD derivative BA was prepared. y-Globulin was hydrolyzed upon incubation with BA, whose half-life was as short as 1 h at 25°C and pH 7 in the presence of excess BA. The rates for hydrolysis of y-globulin by the Cu(II) complex of cyclen itself dissolved in water were also measured. Comparison of rate data collected at the same catalyst concentrations revealed that the proteolytic activity of the Cu(II) complex of cyclen was... 

Chloromethylated cross-linked polystyrene was used to initiate the graft copolymerization of several 2-substituted-2-oxazoline derivatives (130, 131). Allylic chloride from 1-chloro-l,3-butadiene-butadiene copolymer and from poly(vinyl chloride) was used to initiate the graft copolymerization of 2-methyl-2-oxazoline (132. 133). 

Chloromethyl resin, Merrifield resin, a poly-styrene/divinylbenzene resin functionalized with the chloromethyl group introduced by Friedel-Crafts-type chloro-methylation with the aUcoxy-substituted chloromethane in the presence of tin(IV)... 

Anthrylpolyamines 12-15 (Figure 15) were prepared via dmple substitution reactions of 9-(chloromethyl)anthracene. The full emission spectra of 12-15 (all 1 pM) were collected during titration with ds DNA, ss DNA, heparin, and poly-L-glutamate representative titration data from the monitoring of compound 14 at 422 run are drown in Figure 16. Bodi disubstituted anthracenes (14 and 15) exhibit a 6-nm red shift in when bound either to ds DNA or to ss DNA likewise, both monosubstituted anthracenes (12 and 13) show a 14-nm red shift in their emission spectra in the presence of either ds or ss DNA. Interaction of the nucleotide bases with the anthracene is a likely source of the bathochromic shift and the observed CHEQ effect Such n-stacking with ss DNA, seldom observed with intercalating compounds, may result from the favorable entropy effect of electrostatic preassociation (18). 

HO-PEG-OH, NHa-poly (oxyalkylenediamine)-NH2 Hyperbranched poly (p-(chloromethyl)styrene) Williamson ether synthesis or nucleophilic substitution DS Drug release 91... 

The differences in reactivities in poly(vinyl alcohol)s between isotactic meso) and syndiotactic (trans acetals [26-28] is another example. In extending this to model compounds, reactions of stereo isomers of pentane-2,4-diol and heptane-1,4,6-triol with formaldehyde take place much faster for the meso than for the dl-diol portions [26-28]. Even more important are the steric effects imposed by restricted rotations. For instance, quatemizations of chloromethylated polyether sulfmies exhibit decreasing rates at high degrees of substitution. This can be attributed to restricted rotations of the polymeric chains, because this phenomenon is not observed with more flexible chloromethylated polystyrene under identical conditions [23, 24]. 

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