Poly functionalization

Test Compound (0.1% Concentration) Chemical Functionality Poly- ethylene PVC Lopac... 

Sulfonated hydroquinone was used to prepare functional poly(arylene ether ketone)s, which may be used a gas separation membranes.202... 

Amine catalysts, 235 Amine-functionalized poly(arylene ether ketone), 361 Amines... 

This review has shown that the analogy between P=C and C=C bonds can indeed be extended to polymer chemistry. Two of the most common uses for C=C bonds in polymer science have successfully been applied to P=C bonds. In particular, the addition polymerization of phosphaalkenes affords functional poly(methylenephosphine)s the first examples of macromolecules with alternating phosphorus and carbon atoms. The chemical functionality of the phosphine center may lead to applications in areas such as polymer-supported catalysis. In addition, the first n-conjugated phosphorus analogs of poly(p-phenylenevinylene) have been prepared. Comparison of the electronic properties of the polymers with molecular model compounds is consistent with some degree of n-conjugation in the polymer backbone. 

Fig. 13. Pseudorotaxane-terminated dendrimers from diaminobutane-functionalized poly-propylimine dendrimers and CB[6]...

As an example, consider the use of PVPy as a solid poison in the study of poly(noibomene)-supported Pd-NHC complexes in Suzuki reactions of aryl chlorides and phenylboroiuc acid in DMF (23). This polymeric piecatalyst is soluble under some of the reaction conditions employed and thus it presents a different situation from the work using porous, insoluble oxide catalysts (12-13). Like past studies, addition of PVPy resulted in a reduction in reaction yield. However, the reaction solution was observed to become noticeably more viscous, and the cause of the reduced yield - catalyst poisoning vs. transport limitations on reaction kinetics - was not immediately obvious. The authors thus added a non-functionalized poly(styrene), which should only affect the reaction via non-specific physical means (e.g., increase in solution viscosity, etc.), and also observed a decrease in reaction yield. They thus demonstrated a drawback in the use of the potentially swellable PVPy with soluble (23) or swellable (20) catalysts in certain solvents. 

Our objective In this paper is to illustrate the methods for functionalizing poly(arylene ether sulfone). Particular attention will be paid to bromination, nitration, aminatlon, chloromethyl-ation, and aminomethylatlon of 1 and its corresponding model compound. 

Table I. Mn Values of Methacrylate Functional Poly(Dimethyl Siloxane) via Spectroscopic and Osmotic Techniques...

In addition to providing many new precursors to functionalized poly(alkyl/arylphosphazenes), the deprotonation/substitution reactions of these N-silylphosphoranimines serve as useful models for similar chemistry that can be carried out on the preformed polymers. New reactions and experimentation with reaction conditions can first be tried with monomers before being applied to the more difficult to prepare polymeric substrates. A considerable amount of preliminary work [e.g., with the silylated monomers (z z) and polymers (2 o) has demonstrated the feasibility of this model system approach. 

Keywords. Bacterial polyester, Medium-chain-length poly(3-hydroxyalkanoates), Pseudomonas oleovorans, Pseudomonas putida, Functional poly(3-hydroxyalkanoates), Short-chain-length poly(3-hydroxyalkanoates)... 

Thiol end-functionalized poly(2-hydroxyethyl methacrylate-g-ethylene glycol) graft copolymers were synthesized by ATRP copolymerization of... 

Initiators such as (306) initiate the ROP of CL to form telechelic triblock diols.478 Molecular weights approach theoretical values with polydispersities <1.3 and no significant level of transesterification was detected at up to 95% conversions. Alternative bimetallic samarium initiators have been used to synthesize aromatic, cumulene and amine/imine link-functionalized poly(lactones).479... 

Bae Y, Kataoka K (2009) Intelligent polymeric micelles from functional poly(ethylene glycol)-poly(amino acid) block copolymers. Adv Dmg Deliv Rev 61 768-784... 

Gaertner, H.F., and Offord, R.E. (1996) Site-specific attachment of functionalized poly(ethylene glycol) to the amino terminus of proteins. Bioconjugate. Chem. 7, 38-44. 

Horak, D., Karpisek, M., Turkova, J., and Benes, M. (1999) Hydrazide-functionalized poly(2-hydroxye-thyl methacrylate) microspheres for immobilization of horseradish Peroxidase. Biotechnol. prog. 15, 208-215. 

Huang, B., and Tomalia, D.A. (2005) Dendronization of gold and CdSe/cdS (core-shell) quantum dots with tomalia type, thiol core, functionalized poly(amidoamine) (PAMAM) dendrons. J. Lumin. Ill, 215-223. 

Zalipsky, S., and Lee, C. (1992) Use of functionalized poly(ethylene glycol)s for modification of polypeptides. In Poly(Ethylene Glycol) Chemistry Biotechnical and Biomedical Applications (J.M. Harris, ed.), pp. 347-370. Plenum, New York. 

In 1957, Otsu and coworkers reported that the polymer obtained from St with 13 could induce the radical polymerization of second monomers leading to block copolymers [70-74]. Poly(St)-hZock-poly(MMA), poly(St)-hZock-poly (AN), poly(St)-Z Zock-poly(VAc), and poly(St)-hZock-poly(VA) were prepared from the end-functional poly(St) [75], In the photopolymerization of St and MMA with 13, it was also confirmed that the molecular weight of the polymers produced linearly increased with the reaction time, although the reaction mechanism was not ascertained at that time. Thereafter, the poly(St) produced with 13 was confirmed to have two DC end groups, which can further dissociate pho-tochemically [76]. 

Nair et al. studied the kinetics of the polymerization of MMA at 60-95 °C using N,1SP-diethyl-NjW-di(hydroxyethyl)thiuram disulfide (30a) as the thermal in-iferter [142]. The dependence of the iniferter concentration on the polymerization rate was examined. The chain transfer constant of the propagating radical of MMA to 30a was determined to be 0.23-0.46 at 60-95 °C, resulting in the activation energy of 37.6 kj/mol for the chain transfer. Other derivatives 30b-30d were also prepared and used to derive telechelic polymers with the terminal phosphorus, amino, and other functional aromatic groups [143-145]. Thermal polymerization was also investigated with the end-functional poly(St) and poly(MMA) which were prepared using the iniferter 13 [146]. 

Figure 9.14 Chemical structure of 5-enantiomer of the chromophore-functionalized poly(isocyanide).

U. Scherf and K. Mullen, Polyarylenes and poly(arylene vinylenes), 7. A soluble ladder polymer via bridging of functionalized poly(p-phenylene)-precursors, Makromol. Chem., Rapid Commun., 12 489-497, 1991. 

Crooks et al. reported the transfer of amine-functionalized poly(amidoamine) dendrimers into toluene containing dodecanoic acid [198], The method is based on the formation of ion pairs between the fatty acids and the terminal amine-groups. These dendrimer-fatty acid complexes resemble unimolecular inverted micelles and could be used as phase transfer vehicles for the transport of Methyl Orange, an anionic dye molecule, into an organic medium. 

Funfak et al. [39] demonstrated recently that pH-sensitive microbeads based on 8-hydroxypyrene-l,3,6-trisulfonate covalently attached to amino-functionalized poly(hydroxyethylmethacrylate) (0 2.5 pm) can be successfully used to monitor... 

Wang, R, Li, J., Chen, T. and Xu, J. 1998. Sodium sulfonate-functionalized poly(ether ether ketone)s. Macromolecular Chemistry and Physics 199 1421-1426. 

Allcock, H. R., Hofmann, M. A., Ambler, C. M., Lvov, S. N., Zhou, X. Y., Chalkova, E. and Weston, J. 2002. Phenyl phosphonic functionalized poly(aryloxyphosphanes) as proton-conducting membranes for direct methanol fuel cells. Journal of Membrane Science 201 47-54. 

Scheme 6.5 Hydroformylation of 1 -octene as a model reaction for micellar catalysis using tri-phenylphosphine-functionalized poly(2-oxazoline)s as macroligands.

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