Pendant Functional Groups Research Articles

Synthesis and characterization of poly(N-acyl orN-aroyl ethylenimines) containing various pendant functional groups. IV. Poly (N-aroylethylenimines) with allyloxy and 3-hydroxy propyloxy groups

4-Allyloxy phenyl oxazoline was polymerized using methyl 4-nitrobenzene sulfonate as an initiator (M/I = 100/1) in o-dichlorobenzene. The olefin group in the resulting polymer, PAPO, was quantitatively transformed to a (SINGLE BOND)CH2 (SINGLE BOND)CH2 (SINGLE BOND)OH group by (1) hydroborating the olefin group using 9-BBN as a hydroborating agent in CHCl3/THF, and (2) oxidizing the hydroborated polymer. The polymer backbone is very stable in the hydroboration and oxidation environment. Both PAPO and the hydroxylated polymer, PAPO-OH, are crystalline and show birefringence. The PAPO-OH polymer crystallizes slowly due to its bulky side chain and strong interference of hydroxyl group with the packing of polymer molecules. However, once the polymer crystallizes, the side chains are extended and the (SINGLE BOND)OH groups do not hydrogen bond with the carbonyl groups in the polymer backbone. © 1996 John Wiley & Sons, Inc.

Synthesis and characterization of poly(N‐acyl or N‐aroyl ethylenimines) containing various pendant functional groups. III. Copolymers with pendant epoxy and imidazole groups

Poly(N-acylethylenimines) with epoxy or imidazole groups randomly attached to the end of the side chains were synthesized from decenyl/heptyl oxazoline random copolymers. They are named as DH(m/n)–epoxy and DH(m/n)–imidazole, respectively, and the starting polymers are named as DH(m/n), where m and n represent the calculated numbers of monomers with and without epoxy or imidazole groups. The DH(m/n)–epoxy polymers with 20–60 mol % of epoxy crystallize two dimensionally with crystalline polymethylene plane separated by amorphous epoxy groups. The DH(m/n)-imidazole polymers are difficult to crystallize due to the strong interaction between the bulky imidazole group and amide group. Though the imidazole containing polymers are difficult to crystallize, they are good anticorrosion coatings as demonstrated by a preliminary anticorrosion test of the DH(20/80)–imidazole polymer on electrogalvanized steel, zinc/nickel electroplated steel, and hot dipped galvanized steel. © 1996 John Wiley & Sons, Inc.

Synthesis and characterization of poly(N-acyl orN-aroyl ethylenimines) containing various pendant functional groups. III. Copolymers with pendant epoxy and imidazole groups

Synthesis and characterization of poly(N-acyl orN-aroyl ethylenimines) containing various pendant functional groups. III. Copolymers with pendant epoxy and imidazole groups

Synthesis and characterization of poly(N-acyl orN-aroyl ethylenimines) containing various pendant functional groups. I. Copolymers with pendant olefin groups

Decenyl (D) and heptyl (H) oxazolines were copolymerized in o-dichlorobenzene solvent using methyl 4-nitrobenzenesulfonate as an initiator. A series of decenyl/heptyl oxazolines random copolymers (or DH copolymers) with a total degree of polymerization of 100 and narrow molecular weight distribution were obtained. These copolymers are considered as the poly(N-acylethylenimine)s with allyl pendant groups randomly attached to the far end of their polymethylene, (SINGLE BOND)(CH2)7(SINGLE BOND), side chains. The polymers were characterized by NMR, FT–IR. Both DSC and x-ray diffractometer demonstrated that the polymers are highly crystalline. © 1996 John Wiley & Sons, Inc.

Synthesis and characterization of poly(N‐acyl or N‐aroyl ethylenimines) containing various pendant functional groups. II. Copolymers with pendant hydroxyl groups

Synthesis and characterization of poly(N‐acyl or N‐aroyl ethylenimines) containing various pendant functional groups. II. Copolymers with pendant hydroxyl groups

Synthesis and characterization of poly(N‐acyl or N‐aroyl ethylenimines) containing various pendant functional groups. V. Random copolymers of 4‐allyloxy and 4‐methoxy phenyl oxazolines and their adducts with mercaptoacetic acid

4-Methoxyphenyl oxazoline (MPO) was synthesized from 4-methoxybenzonitrile and ethanolamine by using cadmium acetate as a catalyst. 4-Allyloxy phenyl oxazoline (APO) was synthesized from 4-allyloxybenzonitrile, which was made from 4-cyanophenol. A series of random copolymers of APO and MPO over the whole composition range, with an approximate degree of polymerization of 100, were synthesized. They are named as PAM(m/n), where m and n are the total number of APO and MPO monomer units. All the polymers are crystalline and show birefringence. Their melting points decrease with the increase of mole fraction of MPO, from 240°C for PAM(100/0) to 199°C for PAM(20/80), and then increase to 226°C for PAM(0/100). We reacted mercaptoacetic acid with the PAM(m/n) copolymers to generate polar groups that could strongly bond with metal surfaces. They are named as PAM(m/n)-SCH2COOH, which correspond to their starting PAM(m/n) copolymers. They were characterized by NMR, DSC, hot stage melting, water contact angle, peel strength measurements, and some preliminary anticorrosion tests on cold-rolled steel, electrogalvanized steel, and Zi/Ni electroplated steel. © 1996 John Wiley & Sons, Inc.

Synthesis and characterization of poly(N-acyl orN-aroyl ethylenimines) containing various pendant functional groups. V. Random copolymers of 4-allyloxy and 4-methoxy phenyl oxazolines and their adducts with mercaptoacetic acid

4-Methoxyphenyl oxazoline (MPO) was synthesized from 4-methoxybenzonitrile and ethanolamine by using cadmium acetate as a catalyst. 4-Allyloxy phenyl oxazoline (APO) was synthesized from 4-allyloxybenzonitrile, which was made from 4-cyanophenol. A series of random copolymers of APO and MPO over the whole composition range, with an approximate degree of polymerization of 100, were synthesized. They are named as PAM(m/n), where m and n are the total number of APO and MPO monomer units. All the polymers are crystalline and show birefringence. Their melting points decrease with the increase of mole fraction of MPO, from 240°C for PAM(100/0) to 199°C for PAM(20/80), and then increase to 226°C for PAM(0/100). We reacted mercaptoacetic acid with the PAM(m/n) copolymers to generate polar groups that could strongly bond with metal surfaces. They are named as PAM(m/n)-SCH2COOH, which correspond to their starting PAM(m/n) copolymers. They were characterized by NMR, DSC, hot stage melting, water contact angle, peel strength measurements, and some preliminary anticorrosion tests on cold-rolled steel, electrogalvanized steel, and Zi/Ni electroplated steel. © 1996 John Wiley & Sons, Inc.

Synthesis and characterization of poly(N-acyl orN-aroyl ethylenimines) containing various pendant functional groups. II. Copolymers with pendant hydroxyl groups

Poly(N-acylethylenimines) with hydroxyl groups randomly attached to the end of the side chains were synthesized from decenyl/heptyl oxazoline random copolymers. The terminal olefin groups in the polymer side chains react quantitatively with 9-borabicyclo[3.3.1]nonane (9-BBN) in THF solvent. The hydroborated polymers can be oxidized and transformed to the polymers with (SINGLE BOND)OH in their side chains. The polymer backbone is very stable in the hydroboration and oxidation reaction environment. The polymers were named as DH-OH or DM(m/n)-OH, where m and n represent the calculated numbers of monomers with and without the (SINGLE BOND)OH group, respectively. The DH(m/n)-OH copolymers were studied by DSC, wide-angle x-ray diffraction, contact angle measurement, and FT–IR. They are crystalline and show birefringence. In polymers with high concentration of hydroxyl groups, the (SINGLE BOND)OH groups promote polymer crystallization due to their strong interactions. They have very high ΔH of fusion, sharp crystallization peaks, and small supercoolings. Wide-angle x-ray diffraction study of these polymers demonstrated that their alkyl side chains are not fully extended in crystalline domain as those in the DH copolymers. Data from advancing water/ethanol mixture contact angle measurement indicates that most of the (SINGLE BOND)OH groups in the copolymers are buried and the polymer surface is mainly composed of methyl or methylene group. FT–IR study in the carbonyl stretching region proves that the (SINGLE BOND)OH groups can bend back and form hydrogen bonding with the carbonyl groups in the polymer backbone. Though the DH–OH polymers show basically a hydrocarbon surface in a normal environment, both receding water contact angle and peel strength measurements demonstrate that the polymer surfaces can reorganize when they are in contact with a polar liquid. The buried (SINGLE BOND)OH groups can be “pulled” out by polar agents such as water or tape adhesive. © 1996 John Wiley & Sons, Inc.

Polymers with Pendent Functional Groups. II. Investigation on the Chloromethylation of Polystyrene

Abstract The study attempted to establish the optimum reaction conditions for obtaining soluble chloromethylated polystyrene with a transformation degree higher than 50%. A paraformaldehyde and chlorotrimethylsilane mixture as chloromethylation agent and SnCl4 as catalyst were used. The transformation degree followed by the chlorine content depends on the following parameters: temperature, time, and [SnCl4]/[PS] and [Me3ClSi]/[PS] molar ratios.

Enzyme-catalysed polymer modification: reaction of phenolic compounds with chitosan films

One method of synthesizing new materials is to react functional pendant groups on an existing polymer. Here, an enzymatic strategy was investigated as a method of producing new polymers from chitosan. The enzyme used was tyrosinase which is known to oxidize a range of phenolic reactants, yielding reactive o-quinones. The products of this enzymatic oxidation appear to react with, and alter the chemical properties of chitosan. Specifically, it was observed that when thin chitosan films were treated with both tyrosinase and a phenolic reactant, the u.v.-visible spectra and the acid-base properties were markedly altered compared with films that were untreated.

Assembly of Amphiphilic Phenylacetylene Macrocycles at the Air−Water Interface and on Solid Surfaces

The assembly of amphiphilic phenylacetylene macrocycles (PAMs), with molecular structures that vary in terms of the nature and orientation of their pendant functional groups, has been studied on a Langmuir−Blodgett trough and after transfer onto solid substrates. These monolayer films are of interest as two-dimensional host matrices and shape selective membranes whose two-dimensional organization should bring together shape selective compartments. The disk-like PAMs can, in principle, adopt orientations in which the plane of the macrocycle can range from perpendicular (edge-on) to parallel (face-on) at the interface. PAMs functionalized with six hydrophilic groups around the periphery do not prefer the face-on orientation and are most likely tilted, perhaps in a poorly organized state. PAMs that have spatially segregated hydrophilic and hydrophobic groups adopt the edge-on orientation when the hydrophilic moieties are carboxylate groups. In contrast, PAMs appended with acid moieties do not lead to stable monolayers, most likely because they engage in strong intermolecular hydrogen bonding interactions as evidenced by 1H NMR and vapor pressure osmometry of the solutions. Monolayers of the dicarboxylate PAMs were transferred onto fused silica and Si(100) surfaces and these were in turn characterized by contact angle, ellipsometry, absorption FTIR, and angle-resolved X-ray photoelectron spectroscopies. Taken together these characterization experiments strongly support the hypothesis that the dicarboxylate PAMs form a well-ordered and stable two-dimensional array and that they adopt the edge-on configuration with near-vertical orientation of the macrocycle plane.

A Novel Approach to α,β-Unsaturated Acrylated Polymers from Poly(2-methylvinylacetylene) by Homogeneous Catalysis

Polymerization of 2-methylvinylacetylene (VA) is a selective, anion-initiated process affording poly(2-methylvinylacetylene) (PVA) with Mw of 1600−3060 and a polydispersity of 1.5−1.7. The acetylenic groups of PVA can be further functionalized by palladium(II)-catalyzed hydrocarboxylation, hydroesterification, and iodoarene/CO coupling reactions to give new polymers containing pendant functional groups of α,β-unsaturated carboxylic acids, esters, and ketones, respectively. The catalytic processes used here provide unique methods to synthesize these polymers in a stereocontrolled and stereoselective manner. Using the Pd(OAc)2−dppb catalytic system, high conversions (100%) of the pendant acetylenic groups of PVA were realized, affording α,β-unsaturated acid- or ester-containing polymers with >80% selectivity at the terminal position. These polymers are not available by direct polymerization of functionalized monomers. Gel permeation chromatography indicated that neither chain scission nor cross-linking take...

Preparation and Characterization of Au Colloid Monolayers

The design and initial characterization of two-dimensional arrays of colloidal Au particles are reported. These surfaces are prepared by self-assembly of 12 nm diameter colloidal Au particles onto immobilized polymers having pendant functional groups with high affinity for Au (i.e., CN, SH, and NH 2 ). The polymers are formed by condensation of functionalized alkoxysilanes onto cleaned quartz, glass, and SiO 2 surfaces. The assembly protocol is carried out completely in solution: cleaned substrates are immersed in methanolic solutions of organosilane, rinsed, and subsequently immersed in aqueous colloidal Au solutions. Two-dimensional arrays spontaneously form on the polymer surface. The resulting substrates have been characterized by UV-vis spectroscopy, transmission electron microscopy (TEM), and surface-enhanced Raman scattering (SERS). TEM data show that the particles are spatially separated but close enough to interact electromagnetically (small spacing compared to λ). The UV-vis data show that collective particle surface plasmon modes are present in the 650-750 nm region, suggesting that these assemblies are SERS-active. This is indeed the case, with enhancement factors of roughly. Au colloid monolayers possess a set of features that make them very attractive for both basic and applied uses, including uniform roughness, high stability, and biocompatibility

Multifunctional coupling agents for living cationic polymerization. IV. Synthesis of end‐functionalized multiarmed poly(vinyl ethers) with multifunctional silyl enol ethers

AbstractTelechelic (8) and end‐functionalized four‐arm star polymers (9) were synthesized through the coupling reactions of end‐functionalized living poly(isobutyl vinyl ether) (5; DPn ∼ 10) with the bi‐and tetrafunctional silyl enol ethers, H4‐nC[CH2OC6H4C(OSiMe3) = CH2]n (3: n = 2; 4: n = 4). The precursor polymers 5 were prepared by living cationic polymerization with functionalized initiators, CH3CH(Cl)OCH2CH2X(6), in conjunction with zinc chloride in methylene chloride at −15°C. The initiators 6 were obtained by the addition of hydrogen chloride gas to vinyl ethers bearing pendant functional groups X, including acetoxy [OC(O)CH3], styryl (OCH2C6H4‐p‐CH = CH2), and methacryloyl [OC(O)C(CH3) = CH2]. The coupling reactions with 3 and 4 in methylene chloride at −15°C for 24 h afforded the end‐functionalized multiarmed polymers (8 and 9) in high yield (>91%), where those with styryl or methacryloyl groups are new multifunctional macromonomers. © 1994 John Wiley & Sons, Inc.

Template Syntheses and Crystal Structures of Nickel(II) Complexes of Hexaaza Macrocyclic Ligands with Pendant Functional Groups: Formation of a Coordination Polymer

published in Advance ACS Abstracts, October 15, 1994. (1) Hay, R. W.; Pujari, M. P.; Thomas Moodie, W.; Craig, S.; Richens, D. T.; Perotti, A,; Ungaretti, L. J . Chem. Soc., Dalton Trans. 1987, 2605. (2) Barefield, E. K.; Foster, K. A,; Freeman, G. M.; Hodges, K. D. Inorg. Chem. 1986, 25, 4663. (3 ) Tschudin, D.; Basak, A,; Kaden, T. A. Helv. Chim. Acta 1988, 71, 100. (4) Freeman, G. M.; Barefield, E. K.; Van Derveer, D. G. Inorg. Chem. 1984, 23, 3092. ( 5 ) For reviews: (a) Kimura, E. Tetrahedron, 1992, 48, 6175. (b) Bemhardt, P. V.; Lawrance, G. A. Coord. Chem. Rev. 1990,104,297. (c) Kaden, T. A. Comments Inorg. Chem. 1990, IO, 25. (d) Kimura, E. Crown Ethers and Analogous Compounds; Kiraoka, M., Ed.; Elsevier: Amsterdam, 1992; p 381. (6) Lawrance, G. A,; Martinez, M.; Skelton, B. W.; White, A. H. J . Chem. Soc., Dalton Trans. 1992, 823. (7) Kimura, E.; Haruta, M.; Koike, T.; Shinoya, M.; Takenouchi, K.; Iitaka, Y. Inorg. Chem. 1993, 32, 2779. sized by inserting the metal ions in the free ligands which were prepared by rather elaborate many-step procedures. Recently, we have been interested in the macrocyclic complexes containing pendant donors which are capable of intraor intermolecular coordination and tried to synthesize them by the simple one pot template condensation reaction instead of a many-step procedure. Over the last few years, various saturated polyaza multidentate, macrocyclic, and macropolycyclic complexes have been prepared by the template condensation reactions involving formaldehyde and Especially, we have developed a simple procedure for the preparation of the complexes of hexaaza macrocyclic ligand which resembles 1,4,8,11tetraazacyclotetradecane (cyclam). By modifying a previous method, we have synthesized the complexes of macrocyclic (8) Suh, M. P.; Shin, W.; Kim, D.; Kim, S. Inorg. Chem. 1984,23, 618. (9) Suh, M. P.; Kim, D. Inorg. Chem. 1985, 24, 3712. (10) Suh, M. P.; Shin, W.; Kim, H.; Koo, C. H. Inorg. Chem. 1987, 26, (11) Suh, M. P.; Kang, S. Inorg. Chem. 1988, 27, 2544. (12) Jung, S.; Kang, S.; Suh, M. P. Bull. Kor. Chem. SOC. 1989, 10, 362. (13) Suh, M. P.; Shin, W.; Kang, S.-G.; Lah, M. S.; Chung, T. M. Inorg. Chem. 1989, 28, 1602. (14) Suh, M. P.; Kang, S. V. Goedken, Park, S. Inorg. Chem. 1991, 30, 365. (15) Bernhardt, P. V.; Curtis, L. S.; Curtis, N. F.; Lawrance, G. A,; Skelton, B. W.; White, A. H. Aust. J . Chem. 1989, 42, 797. (16) Fabbrizzi, L.; Lanfredi, A. M. M.; Pallavicini, P.; Perotti, A,; Taglitti, A.; Ugozzoli, F. J . Chem. Soc., Dalton Trans. 1991, 3263. (17) Blas, A. D.; Santis, G. D.; Fabbrizzi, L.; Liccelli, M.; Lanfredi, A. M. M.; Pallacicini, P.; Poggi, A.; Ugozzoli, F. Inorg. Chem. 1993, 106. 1846. 0020166919411333-5509$04.50/0

Specialty and advanced polymers by carbocationic macromolecular engineering

AbstractThis study briefly surveys a variety of new advanced polymeric materials and controlled synthetic processes available by carbocationic macromolecular engineering techniques and having potential commercial interest. These recent developments, mainly by living carbocationic polymerization, have led to new opportunities in polymerization process control, and in designing microstructure, functionality, molecular weight and molecular weight distribution (MWD) and thus properties of a wide variety of unique polymer systems. The fundamentals of these new emerging technologies and the novel materials offered by them, such as macromonomers, telechelics, polymers with pendant functional groups (liquid crystalline homo‐ and co‐polymers, non‐linear optical materials etc.), star‐shaped macromolecules, block and graft copolymers, high temperature polymers, and specialty networks (amphiphilic networks and rubber toughened bone cements) as potential biomaterials will be overviewed.

Synthesis of biodegradable polyesteramides with pendant functional groups

AbstractMorpholine‐2,5‐dione derivatives having substituents with benzyl‐protected carboxylic acid, benzyloxycarbonyl‐protected amine and p‐methoxy‐protected thiol groups, respectively, were prepared in 29–58% yield by cyclization of the corresponding N‐[(2RS)‐bromopropionyl]‐L‐amino acids. Polyesteramides with protected pendant functional groups were obtained by ring‐opening copolymerization of either ϵ‐caprolactone or DL‐lactide with morpholine‐2,5‐dione derivatives having protected functional substituents. The copolymerizations were carried out in the bulk at 130°C using stannous octoate as an initiator and using low mole fractions (0,05, 0,10 and 0,20) of morpholine‐2,5‐dione derivatives in the feed. The molecular weight of the resulting copolymers ranged from 1,4 to 8,3 · 104. The ring‐opening homopolymerization of morpho‐line‐2,5‐dione derivatives with protected functional substituents was not successful. Polyesteramides with either pendant carboxylic acid groups or pendant amine groups were prepared by catalytic hydrogenation of the corresponding protected copolymers. Treatment of copolymers having pendant p‐methoxybenzyl‐protected thiol groups with trifluoromethanesulfonic acid resulted not only in the removal of the p‐methoxybenzyl group but also in severe degradation of the copolymers, due to acidolysis of main‐chain ester bonds.

Initiation and termination mechanisms in kinetic gelation simulations

AbstractA kinetic gelation simulation is presented which includes a distinct initiator species decaying exponentially with time such that the rate of initiation varies as in an actual polymerization. The effects of the initiator quantity and the initiator decay constant on the polymerization are shown along with the effect of varying the probability that two radicals on adjacent sites will terminate. Varying the initiation rate and termination probability are examined in order to determine their influence on the trapping of radicals, the relative reactivity of pendant functional groups, and the overall structure of the polymer. In general it appears that the incorporation of an initiator enables the simulation to more adequartely describe the polymerization reaction, particularly time‐dependent phenomena such as rate of reaction and radical concentrations.

Synthesis and properties of photoreactive polysiloxanes containing pendant functional groups

Abstract

New polymer syntheses, 36. Functionalized aromatic polyethers derived from 4′‐substituted 2,6‐difluorobenzophenones

AbstractToluene, anisol, thioanisol, 4‐phenoxyacetophenone and N,N‐diacetyl‐4‐phenoxyaniline were subjected to a Friedel‐Crafts acylation with 2,6‐difluorobenzoyl chloride. The resulting 4′‐substituted 2,6‐difluorobenzophenones 1a–e were condensed with trimethyl silylated Bis‐phenol‐A (2) to yield homopolyethers with pendant functional groups. A series of copolyethers was analogously prepared by concondensation of 4′‐substituted 2,6‐difluorobenzophenones with a diphenol and 4,4′‐difluorobenzophenone (4a) or bis(4‐fluorophenyl) sulfone (4b), and another series by cocondensation of 2 with mixtures of 4′‐substituted 2,6‐difluorobenzophenones and 2,6‐difluorobenzonitrile (8) or 2,6‐difluoropyridine (9). All polyethers were characterized by inherent viscosities, elemental analyses and DSC‐measurements. In individual cases GPC‐measurements, thermomechanical and thermogravimetric analyses were conducted. The quantitative polymer‐analogous oxidation of methylthio groups into methylsulfinyl and finally into methylsulfonyl groups is demonstrated.