Higher aliphatic aldehyde polymers,VII: poly(n-decaldehyde)

n-Decaldehyde (DA) was polymerized to crystalline poly(n-decaldehyde) (PDA) of reasonable molecular weight in methylcyclohexane (MCH) solvent with lithiumtert-butoxide (LTB) as the initiator under carefully controlled temperature conditions. The polyacetal structure ofPDA was established by IR and PMR spectroscopy as well as by the characteristic degradation of the polymer in the presence of 2,4-dinitrophenylhydrazine.PDA had the dual melting behavior typical of aliphatic polyaldehydes with four or more side chain carbon atoms. The DSC scans of crystallinePDA in the first, or side chain, transition region showed as many as three endothermic peaks between 45 and 65°C. The X-ray diffraction pattern of crystalline PDA was similar to that which had been observed for other polyaldehydes but with a larger unit cell.PDA was extruded at 53°C in a capillary rheometer and gave a filament whose X-ray diffraction pattern indicated medium orientation effects.

---

Zusammenfassung Die Polymerization vonn-Decaldehyd zu einem krystallinen Polymeren von mittlerem Molekulargewicht wurde mit Lithium-tert-butylat in Methylcyclohexan unter genauer Temperaturkontrolle durchgeführt. Poly(n-decaldehyd) (PDA) wurde mittels spektroskopischen Methoden (IR und PMR) charakterisiert, und durch Abbau in der Gegenwart von 2,4-Dinitrophenylhydrazin wurde die Polyacetalstructur des Polymeren bestätigt.PDA hat einen Doppelschmelzpunkt ähnlich anderer aliphatischer Polyaldehyde mit mehr als vier Kohlenstoffatome in der Seitenkette.DSC-Untersuchungen zeigten in der ersten Übergangsregion, der der Seitenkettenkristallisation, daß drei endotherme Spitzen zwischen 45 und 65° beobachtet werden konnten. DasDebye-Scherrer-Diagramm des krystallinenPDA war ähnlich dem anderer Polyaldehyde, aber mit größerer Einheitszelle.PDA wurde bei einer Temperatur von 53°C in einem Rheometer extrudiert und gab Fasern, deren Röntgenstreuung mittlere Orientierung zeigte.

---

---

Part Vl:J. Starr andO. Vogl, J. Polymer Sci., Polym. Chem. Ed. (in press.).     

Organosilane polymers. I. Poly(dimethylsilylene)

Poly(dimethylsilylene) higher polymers prepared by alkali metal coupling of purified dimethyldichlorosilane were found to be high melting, largely crystalline polymers, soluble in solvents at temperatures above 200°C.     

Poly(organophosphazenes)--unusual new high polymers.

An inorganic-backbone high polymer system based on alternating phosphorus and nitrogen atoms promises to solve many of the problems hitherto associated with conventional organic polymers. The chemistry, structure, biomedical, and technological aspects of these polymers are reviewed.     

聚离子液体水凝胶用于中性水中Cr(VI)的去除

随着经济的快速发展,水污染已成为全球关注的紧迫问题。其中,Cr（VI）在废水中含量较高且毒性较强,可引起多种严重疾病。而大多数污染地表水和地下水的pH往往是接近中性的。因此,开发具有近中性pH值下有效去除Cr（VI）的吸附剂对生态系统和公众健康至关重要。本文设计并制备了具有不同结构的三氮唑鎓聚离子液体水凝胶,并将其应用于CrO42-的吸附和释放。该水凝胶可在中性条件下实现水中CrO42-的100%去除,最大吸附量高达356 mg/g。等温吸附结果表明,在较低浓度下CrO42-在聚离子液体水凝胶中为单层吸附。此外,可进一步通过离子交换将吸附于水凝胶中的CrO42-释放出来,实现吸附剂的再生。     

Organosilane polymers. II. Poly(ethylmethyl-co-dimethylsilylene) and poly(methylpropyl-co-dimethylsilylene)

Polydimethylsilylene is a largely crystalline, high-melting polymer that is soluble only above 200°C and does not thermoform below its decomposition temperature. Introduction of ethyl and propyl substituents into the linear silylene system by random copolymerization of dimethylsilylene with ethylmethyl- and methylpropylsilylenes leads to tractable polymers that are soluble in common solvents at normal ambient temperatures.     

Poly(amidoamine-organosilicon) (PAMAMOS) multi-arm star polymers

A new class of hydrophilic core – hydrophobic arms multi-arm star polymers is described: the first such materials to have silicon located in the side arms. They belong to the broad family of radially layered copolymeric amidoamine-organosilicon (PAMAMOS) dendritic macromolecules and may be viewed as nanostructured, covalently bonded, inverse micelles. Two types of hydrophobic, silicon-containing arms have been used, one based on polydimethylsiloxane (PDMS) and another based on predominantly alkyl chains attached by organosilicon chemistry to the hydrophilic polyamidoamine (PAMAM) core. The former polymers are synthesized by a reaction of amine-terminated PAMAMs by mono-functional epoxy PDMS, while the latter are obtained by haloalkylation of the same PAMAMs with a suitable unsaturated silane followed by alkylthiol addition. The Langmuir film behavior of the multi-arm star polymers with PDMS arms is described and rationalized in comparison with that of other hydrophobically modified PAMAM dendrimers reported in the literature. Their uptake of Cu²⁺ from aqueous solutions is also described.     

Dioxouranium(VI) complexes of aliphatic (mono- and di-) hydrazone-oximes

Summary Uranyl acetate dihydrate reacts with several hydrazone-oximes, derived from aliphatic (mon-annd di-) hydrazides and 2,3-butanedione monoxime in the absence of NaOAc, to form complexes of general formulae [UO₂(HL)₂] and [UO₂(HL)₂SZ] (where H₂L=aliphatic acid monohydrazone-oximes; S=EtOH and Z=H₂O). With aliphatic acid dihydrazone and monomaleoyl-hydrazone-oximes, different complexes have been synthesized in 50% EtOH and in the absence of NaOAc. The products have been characterized by elemental analyses, molar conductivities, spectral (u.v., i.r., n.m.r.), pH, conductometric titrations, molecular weights and magnetic measurements. I.r. spectral data indicate that the aliphatic hydrazone-oximes, except monomaleoyl-hydrazone-oxime, behave in a similar way to tridentate ligandsvia the azomethine nitrogen and the NOH groups, with replacement of a hydrogen atom from the latter group. On the other hand, malonyl dihydrazone- and adipoyldihydrazone-oximes coordinate in a bi-, and tridentate manner, respectively, towards one uranyl ion, while monomaleoyl- and oxaloyldihydrazone-oximes behave in a penta-and hexadentate fashion, respectively, towards two uranyl ions. Elemental analyses, molecular weight measurements as well as spectral data confirm the existence of a binuclear complex for monomaleoyl- and oxaloyldihydrazone-oximes, whereas a monomer for the rest. Finally, the role of solvent, absence of NaOAc and the type of ligand on the structure of the complexes are discussed.     

New amphiphilic polymers: Poly(N-alkylacrylamide-CO-vinylpyridinium)

A series of new amphiphilic polymers containing various amounts of N-methyl-4-vinylpyridinium units as hydrophilic part and N-dodecylacrylamide or N-decylacrylamide units as hydrophobic part have been prepared by quaternizing the cognate copolymers. Their behaviour in aqueous solutions has been studied by viscometry, as well as by fluorescence spectroscopy and tensiometry. Results are discussed in detail and a conformational model of the macromolecules at the interface (water/methylcyclohexane) is proposed in relation to the formation of microdomains in the aqueous media.     

Poly(ethylene glycol)-based shape-memory polymers

Poly(ethylene glycol) (PEG) blends photo-curable and thermal activated shape-memory polymers (SMPs), with different activation temperature (T_switch), have been synthesized and characterized. PEG blends with different molecular weights were chain-end functionalized with isocyanate ethyl methacrylate and photo-cured with UV lamp. Degree of cross-linking of the blend network, determined by gel content measurement, resulted as higher than 95%. The thermal and thermomechanical properties of these SMPs PEG blends were characterized by differential scanning calorimetry and dynamic mechanical analysis. The shape-memory properties of the networks were quantified using thermomechanical three-point bending experiments and showed strain fixity rates higher than 99% and a minimum strain recovery ratio of 82%.     

Conformational properties of polar polymers. II. Poly(vinylidene chloride)

A recently developed polarization model for representing polar bond effects in conformational energy calculations is applied to poly(vinylidene chloride) (PVDC). The geometries and conformational energies of a number of conformers of 2,2,4,4,6,6-hexachloroheptane were calculated. The geometries were found to be similar to the hydrocarbon analog polyisobutylene (PIB) in that steric crowding results in the usual T, G, G′ states being split into + or ? distortions of the torsional angles away from the traditional values. Only distortions of the same sign occur in the same pair of bonds interior to CCl₂ groups. Distortions of G states towards eclipsed were found to be much more stable than those away. The interior skeletal valence angle is also distorted to an unusually large value, ca. 121°. The calculated dipole moments were used to infer a group moment for CCl₂ of 1.56 D. The calculated conformational energies were fitted by linear combinations of interaction parameters representing the stabilities of G₊, G_? bonds (relative to T₊, T_?) and the interactions between bonds across intervening CCl₂ groups. These parameters were used in statistical mechanical calculations of the characteristic and dipole-moment ratios. In order to make comparison with experiment, the dipole-moment/repeat unit of a 90% (by weight) PVDC copolymer with PVC was measured and found to be 1.42 ± 0.05 D. From this, the dipole-moment ratio for PVDC homopolymer is inferred to be ca. 0.8. The characteristic and dipole-moment ratios calculated from the interaction parameter set were somewhat too high but adjustment of the gauche energies downward brings the calculated ratios into agreement with experiment. The same statistical model along with energy parameters previously calculated also gives agreement with experiment for the characteristic ratio of PIB. The calculated geometries are in agreement with the conformation in the crystal being ? (T₊G′₊T_?G_?)? .     

Conformational properties of polar polymers. I. Poly(vinyl chloride)

A recently developed method for including polar bonds in conformational energy calculations is applied to poly(vinyl chloride). Inductive effects on dipole moments and the effects of intervening atoms on electrostatic interaction energies are represented by polarizability centers in conjunction with bond centered dipoles. Solvation energies are estimated by means of a continuum dipole–quadrupole electrostatic model. Calculated energies of a number of conformations of meso and racemic 2,4-dichloropentane and the iso, syndio, and hetero forms of 2,4,6-trichloroheptane give satisfactory representations of isomer and conformer populations. Electrostatic effects are found to be quite important. However they appear to be effectively of sufficiently short range that the calculated conformer energies are found to be fit well by a linear combination of interaction parameters (consisting of gauche, skew chlorine, four-bond CH₂…CH₂, CH₂…Cl, and Cl…Cl interactions) conventional to vinyl polymers and a special four-bond interaction that arises when the bond sequence Cl? CH? CH²? CH? Cl is (nearly) coplanar. These interaction parameters when assembled into statistical weight matrices lead to calculated values of both the characteristic ratio and the dipole moment ratio in satisfactory agreement with experiment. Least energy paths for transitions between the most stable conformations are also calculated.     

Porosity inherent to chemically crosslinked polymers. Poly(N-vinylimidazole) hydrogels

Swollen polymer networks exhibit multiscale pores filled with solvent. Such porosity, inherent to cross-linked polymers, determines some of their most relevant physical properties and applications. In this research, several samples of chemically crosslinked poly(N-vinylimidazole) were synthesized with the same permanent crosslinking density at two different conversions, and their inherent porosity was characterized on freeze-dried specimens by SEM, TEM and nitrogen physisorption. It was thus found that all of the samples showed pores, both on the nanometer and the micrometer scales, whose dimensions were mostly equal to or larger than the mesh size of the primary polymer network (22 nm) and whose volume and specific surface decreased with increasing conversion. Micropores have, in all cases, a very minor contribution. Samples synthesized with the largest comonomer concentrations show quasi-spherical mesopores (90 nm average diameter at any conversion) and macropores (from 5 to 10 microm with increasing conversion), whereas the mesopores of samples synthesized with the largest crosslinker ratios were channel-like (150 nm) and the macropores were interconnected contiguous voids (3 microm). Samples with intermediate compositions exhibit the lowest porosity due, mostly, to interconnected mesopores. The differences in shape were ascribed to the mechanism of phase separation, taking place during polymerization, even for samples that are transparent following polymerization. The inherent porosity is a significant source of spatial inhomogeneity, which contributes to the increase in turbidity. Light scattering decreases with increasing ionization when the degree of protonation is greater than 10%. An important consequence of the inherent porosity is that the degrees of swelling determined either gravimetrically or through size measurements are not equivalent.     

Poly(p-phenylenes) with well-defined side chain polymers

1,4-Dibromo-2,5-bis(bromomethyl)benzene and benzene-2,5-dibromomethyl-1,4-bis(boronic acid propanediol diester) were used as bifunctional initiators in Atom Transfer Radical Polymerization (ATRP) of styrene or in cationic ring opening polymerization (CROP) of tetrahydrofuran in conjunction with CuBr /2,2'-bipyridine or AgSbF₆, respectively. The resulting well-defined macromonomers with low polydispersities, bearing functional groups as bromine or boronic ester were used in Suzuki or Yamamoto type couplings, leading to poly(p-phenylene)s (PPPs) with polystyrene (PSt), polytetrahydrofuran (PTHF) or alternating PSt/PTHF side chains. The new polymers were characterized by GPC, ¹H-NMR, ¹³C-NMR, IR and UV analysis. Thermal behavior of the precursors PSt or PTHF macromonomers and the final polyphenylenes were investigated by TGA and DSC analyses and compared.     

Extraction of uranium(VI) and plutonium(IV) with some aliphatic amides

Extraction of uranium(VI) and plutonium(IV) has been studied with N,N-dibutyl derivatives of hexanamide (DBHA), octanamide (DBOA) and decanamide (DBDA) at various fixed temperatures of 20, 30, 40 and (50±0.1)°C. The equilibrium constants for the uptake of nitric acid (K_h, a measure of their relative basicities) by these amides were evaluated by the usual method. The equilibrium constants for the extraction of uranium as well as plutonium with all the three amides follow their order of basicity (K_h) viz. DBHA (0.09)<DBOA (0.10)<DBDA (0.13) with log K values of 1.31, 1.43 and 1.73 for uranium and 3.55, 3.65 and 4.17 for plutonium, respectively. It has been observed that whereas uranium(VI) is extracted as a disolvate (similar to TBP and sulfoxides), plutonium(IV) has been found to be extracted as a trisolvate. The thermodynamic parameters evaluated by the usual temperature coefficient method indicate that the extraction reactions of uranium as well as plutonium are stabilized by negative enthalpy change only.     

Functional polymers. XIV. Grafting of 2(2-hydroxy-5-vinylphenyl)2H-benzotriazole onto polymers with aliphatic groups

Successful grafting of 2(2-hydroxy-5-vinylphenyl)2H-benzotriazole onto saturated aliphatic C? H groups of polymers has been accomplished. When the grafting reaction was carried out in chlorobenzene at 150–160°C with di-tertiary butylperoxide as the grafting initiator, grafts as high as 20–30% at grafting efficiencies of 50 and 80% have readily been obtained. It was very important to carry out the grafting reaction in tubes sealed under high vacuum since trace amounts of oxygen cause complete inhibition of the grafting reaction by the phenolic monomer. Grafting reactions were carried out on a variety of different polymers including atactic polypropylene, ethylene/vinyl acetate copolymer, poly(methyl methacrylate), poly(butyl acrylate), and polycarbonate.     

Sulfur-containing polymers. VI. Preparation of poly[alkylene bis(oxycarbonyl) disulfides] and related polymers

Poly[alkylene bis(oxycarbonyl) disulfides] have been prepared for the first time by the reductive coupling of alkylene bis(oxycarbonylsulfenyl chlorides). Potassium iodide and a variety of transition metals or their salts were employed as reducing agents. Of these potassium iodide and cuprous chloride gave the best results. Pyrolysis, desulfurization. and thiol-induced fragmentation of the polymers have been studied. Homologous polymers, i.e., monosulfide polymer, trisulfide polymer, and tetrasulfide polymer, have been also synthesized. Monosulfide and disulfide polymers were highly crystalline solids. Trisulfide polymer was a white solid with a low degree of crystallinity. These polymers were soluble in chloroform and dichloromethane. Tetrasulfide polymer was a crystalline yellow solid and was soluble only in HMPA.     

Anionic exchange studies on uranium(VI) in aliphatic dicarboxylic acids

Summary Uranium (VI) forms anionic complexes with aliphatic dicarboxylic acids namely oxalic, succinic and adipic acids. These complexes are stable in solutions of p_H up to 5 and retained quantitatively on Lewatit MN (Cl^–). The break-through capacities of the ion exchange column used are given for the different uranyl complexes. Li, Cu²⁺, Ni, Co, Cr³⁺, Fe³⁺, Al, Mn²⁺, Th, Zr, Ce⁴⁺ andPO₄ ^3– which may interfere with uranium are tested under the prescribed conditions in order not to affect uranium determination.Thorium and zirconium form anionic oxalate complexes in 1% oxalic acid-ammonium hydroxide solution of p_H range 2.5–5 and are retained quantitatively on Lewatit MN (Cl^–). 0.4 N hydrochloric acid solution is used for eluting uranium or zirconium while thorium is eluted with 4–5 N hydrochloric acid solution.

---

Zusammenfassung Uran(VI) bildet mit aliphatischen Dicarbonsäuren (Oxal-, Bernstein, Adipinsäure) anionische Komplexe, die in Lösung bis zu p_H 5 beständig sind und von Lewatit MN (Cl^–) quantitativ zurückgehalten werden. Die Durchbruchskapazitäten der verwendeten Austauschersäule für die einzelnen Urankomplexe werden angegeben. Störungen durch Li, Cu²⁺, Ni, Co, Cr³⁺, Fe³⁺, Al, Mn²⁺, Th, Zr, Ce⁴⁺ und PO₄ ^3– werden untersucht. Thorium and Zirkonium bilden anionische Oxalatkomplexe in 1%iger Oxalsäurelösung, die mit Ammoniak auf p_H 2,5 bzw. 5 eingestellt ist; diese Komplexe werden von Lewatit MN (Cl^–) quantitativ zurückgehalten. Uran oder Zirkonium werden mit 0,4 n Salzsäure, Thorium mit 4–5 n Salzsäure eluiert.