Polystannanes are organotin compounds with the formula (R2Sn)n. These polymers have been of intermittent academic interest; they are unusual because heavy elements comprise the backbone. Structurally related but better characterized (and more useful) are the polysilanes (R2Si)n.
Oligo- or polystannanes were first described by Löwig in 1852, [1] only 2 years after Edward Frankland's report on the isolation of the first organotin compounds. [2] Löwig's route involved treating an Sn/K and Sn/Na alloys with iodoethane, in the presence of quartz sand which was used to control the reaction rate. Products with elemental compositions close to those of oligo(diethylstannane)s or poly(diethylstannane) were obtained. Cahours obtained similar products and attributed the formation of the so-called "stannic ethyl" to a reaction of the Wurtz type. [3] Already in 1858, "stannic ethyl" was formulated as a polymeric compound denoted with the composition n(SnC4H5). [4] In 1917 Grüttner, [5] who reinvestigated results on hexaethyl-distannanes(H5C2)3Sn-Sn(C2H5)3 (reported by Ladenburg in 1870) confirmed the presence of Sn-Sn bonds and predicated for the first time that tin could form chain like compounds. [6] In 1943, it was postulated that “diphenyltin” exists as a type of polymeric material because of its yellow color, [7] and indeed a bathochromic shift of the wavelength at maximum absorption with increasing number of Sn atoms was found later in the case of oligo(dibutylstannane)s comprising up to 15 Sn atoms. [8]
The Wurtz reaction is still used for the preparation of poly(dialkylstannane)s. Treatment of dialkyltin dichlorides with sodium lead to polystannanes of high molar mass, however, in low yields and with formation of (cyclic) oligomers. [9] [10] Other efforts to prepare high molar mass polystannanes by electrochemical reactions [11] or by catalytic dehydropolymerization of dialkylstannanes (R2SnH2) were also made. [10] [12] Unfortunately, frequently, the polymers prepared by those methods were not isolated and typically contained significant fractions of cyclic oligomers.
Dialkytin dihydrides (R2SnH2) were reported in 2005 to undergo dehydropolymerization in the presence of Wilkinson’s catalyst. This method afforded polystannanes without detectable amounts of "cyclic"-byproducts. The polymers were yellow with number average molar masses of 10 to 70 kg/mol and a polydispersity of 2 – 3. [13] By variation of the catalyst concentration the molar masses of the synthesized polymers could be adjusted. A strong influence of the temperature on the degree of conversion was observed. Determination of the molar mass at different degrees of conversion indicated that polymerization did not proceed according to a statistical condensation mechanism, but, likely, by growth onto the catalyst, e.g. by insertion of SnR2-like units.
The poly(dialkylstannane)s were found to be thermotropic and displayed first-order phase transitions from one liquid-crystalline phase into another or directly to the isotropic state, depending on the length of the side groups. More specifically, poly(dibutylstannane) for example showed an endothermic phase transition at ~0 °C from a rectangular to a pure nematic phase, as determined by X-ray diffraction. [14]
Like polysilanes, polystannanes are semi-conductive. Temperature-dependent, time-resolved pulse radiolysis microwave conductivity measurements of poly(dibutylstannane) yielded values of charge-carrier mobilities of 0.1 to 0.03 cm2 V−1 s−1, which are similar to those found for pi-bond-conjugated carbon-based polymers. By partial oxidation of the material with SbF5 conductivities of 0.3 S cm−1 could be monitored. [15]
The liquid-crystalline characteristics of the poly(dialkylstannane)s permitted facile orientation of these macromolecules, for instance, by mechanical shearing or tensile drawing of blends with poly(ethylene). Poly(dialkylstannane)s with short side groups invariably arranged parallel to the external orientation direction, while the polymers with longer side groups had a tendency to order themselves perpendicular to that axis.
In chemistry, catenation is the bonding of atoms of the same element into a series, called a chain. A chain or a ring shape may be open if its ends are not bonded to each other, or closed if they are bonded in a ring. The words to catenate and catenation reflect the Latin root catena, "chain".
Poly(p-phenylene) (PPP) is made of repeating p-phenylene units, which act as the precursor to a conducting polymer of the rigid-rod polymer family. The synthesis of PPP has proven challenging, but has been accomplished through excess polycondensation with the Suzuki coupling method.
Organotin chemistry is the scientific study of the synthesis and properties of organotin compounds or stannanes, which are organometallic compounds containing tin carbon bonds. The first organotin compound was diethyltin diiodide, discovered by Edward Frankland in 1849. The area grew rapidly in the 1900s, especially after the discovery of the Grignard reagents, which are useful for producing Sn–C bonds. The area remains rich with many applications in industry and continuing activity in the research laboratory.
Polypropylene glycol or polypropylene oxide is the polymer of propylene glycol. Chemically it is a polyether, and, more generally speaking, it's a polyalkylene glycol (PAG) H S Code 3907.2000. The term polypropylene glycol or PPG is reserved for polymer of low- to medium-range molar mass when the nature of the end-group, which is usually a hydroxyl group, still matters. The term "oxide" is used for high-molar-mass polymer when end-groups no longer affect polymer properties. Between 60 and 70% of propylene oxide is converted to polyether polyols by the process called alkoxylation.
Polyphosphazenes include a wide range of hybrid inorganic-organic polymers with a number of different skeletal architectures with the backbone P-N-P-N-P-N-. In nearly all of these materials two organic side groups are attached to each phosphorus center. Linear polymers have the formula (N=PR1R2)n, where R1 and R2 are organic (see graphic). Other architectures are cyclolinear and cyclomatrix polymers in which small phosphazene rings are connected together by organic chain units. Other architectures are available, such as block copolymer, star, dendritic, or comb-type structures. More than 700 different polyphosphazenes are known, with different side groups (R) and different molecular architectures. Many of these polymers were first synthesized and studied in the research group of Harry R. Allcock.
Dendronized polymers are linear polymers to every repeat unit of which dendrons are attached. Dendrons are regularly branched, tree-like fragments and for larger ones the polymer backbone is wrapped to give sausage-like, cylindrical molecular objects. Figure 1 shows a cartoon representation with the backbone in red and the dendrons like cake slices in green. It also provides a concrete chemical structure showing a polymethylmethacrylate (PMMA) backbone, the methyl group of which is replaced by a dendron of the third generation.
A stannide can refer to an intermetallic compound containing tin combined with one or more other metals; an anion consisting solely of tin atoms or a compound containing such an anion, or, in the field of organometallic chemistry an ionic compound containing an organotin anion
Polymers with the ability to kill or inhibit the growth of microorganisms such as bacteria, fungi, or viruses are classified as antimicrobial agents. This class of polymers consists of natural polymers with inherent antimicrobial activity and polymers modified to exhibit antimicrobial activity. Polymers are generally nonvolatile, chemically stable, and can be chemically and physically modified to display desired characteristics and antimicrobial activity. Antimicrobial polymers are a prime candidate for use in the food industry to prevent bacterial contamination and in water sanitation to inhibit the growth of microorganisms in drinking water.
Catalytic chain transfer (CCT) is a process that can be incorporated into radical polymerization to obtain greater control over the resulting products.
A high-refractive-index polymer (HRIP) is a polymer that has a refractive index greater than 1.50.
IUPAC Polymer Nomenclature are standardized naming conventions for polymers set by the International Union of Pure and Applied Chemistry (IUPAC) and described in their publication "Compendium of Polymer Terminology and Nomenclature", which is also known as the "Purple Book". Both the IUPAC and Chemical Abstracts Service (CAS) make similar naming recommendations for the naming of polymers.
The dehydrogenative coupling of silanes is a reaction type for the formation of Si-Si bonds. Although never commercialized, the reaction has been demonstrated for the synthesis of certain disilanes as well as polysilanes. These reactions generally require catalysts.
Polybutylene succinate (PBS) is a thermoplastic polymer resin of the polyester family. PBS is a biodegradable aliphatic polyester with properties that are comparable to polypropylene.
Tetramethylurea is the organic compound with the formula (Me2N)2CO. It is a substituted urea. This colorless liquid is used as an aprotic-polar solvent, especially for aromatic compounds and is used e. g. for Grignard reagents.
2-Ethyl-2-oxazoline (EtOx) is an oxazoline which is used particularly as a monomer for the cationic ring-opening polymerization to poly(2-alkyloxazoline)s. This type of polymers are under investigation as readily water-soluble and biocompatible materials for biomedical applications.
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1-Vinylimidazole is a water-soluble basic monomer that forms quaternizable homopolymers by free-radical polymerization with a variety of vinyl and acrylic monomers. The products are functional copolymers, which are used as oil field chemicals and as cosmetic auxiliaries. 1-Vinylimidazole acts as a reactive diluent in UV lacquers, inks, and adhesives.
Itaconic anhydride is the cyclic anhydride of itaconic acid and is obtained by the pyrolysis of citric acid. It is a colourless, crystalline solid, which dissolves in many polar organic solvents and hydrolyzes forming itaconic acid. Itaconic anhydride and its derivative itaconic acid have been promoted as biobased "platform chemicals" and bio- building blocks.) These expectations, however, have not been fulfilled.
β-Butyrolactone is the intramolecular carboxylic acid ester (lactone) of the optically active 3-hydroxybutanoic acid. It is produced during chemical synthesis as a racemate. β-Butyrolactone is suitable as a monomer for the production of the biodegradable polyhydroxyalkanoate poly(3-hydroxybutyrate) (PHB). Polymerisation of racemic (RS)-β-butyrolactone provides (RS)-polyhydroxybutyric acid, which, however, is inferior in essential properties (e.g. strength or degradation behaviour) to the (R)-poly-3-hydroxybutyrate originating from natural sources.
Polyfullerene is a basic polymer of the C60 monomer group, in which fullerene segments are connected via covalent bonds into a polymeric chain without side or bridging groups. They are called intrinsic polymeric fullerenes, or more often all C60 polymers.