Handbook of Polyolefins, Second Edition, (Plastics Engineering (Marcel Dekker, Inc.), 59.)
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This is achieved using bicyclic monomers. The monomers are readily obtained from the Diels-Alder reactions of substituted olefins with cyclopentadiene. This route is effective also for fluorinated monomers. These types of monomers undergo a ROMP with a variety of one component and two-component initiator systems.
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A wide variety of fluorinated monomers has been investigated with respect to the ability to undergo ROMP. Examples are shown in Figure 1. We will summarize additives for thermoplastic metathesis polymers. Plasticizers include tricresyl phosphate and trixylyl phosphate. Foaming agents can be added in the case of using the polymers for wires, which require low dielectric constant and low dielectric loss tangent, such as communication cables, coaxial cables for computers and high-frequency cables. Flame retardants are preferably added for wires, such as highvoltage power cables through with a large quantity of current flows.
Antioxidants include phenolic antioxidants, phosphorus antioxidants and sulfur antioxidants. Near infrared absorbers include cyanin compounds, pyrylium compounds, phthalocyanine compounds, and dithiol metal complexes.
Handbook of Polyolefins, Second Edition, (Plastics Engineering (Marcel Dekker, Inc.), 59.)
Antistatic agents include long chain alkyl alcohols and fatty acid esters with polyhydric alcohols. Stearyl alcohol and behenyl alcohol are the especially preferred compounds. Anti-fogging agents include sorbitan fatty acid esters and glycerin fatty acid esters.
Metathesis Polymers 1.
Handbook of Engineering and Specialty Thermoplastics: Polyolefins ...
Further, optical applications such as plate lenses, including Fresnel lenses have been described 6. In comparison to poly ethylene PE and polypropylene PP , they show a very low gas permeability. They are used for blister packaging in pharmacy applications and for flexible films for food packaging. Multilayer films consisting of PP outer layers and a cyclic olefin copolymer are in use. Crosslinking agents, foaming agents, flame retardants, and other polymers can be added to the formulation 6. As crosslinking agents, organic peroxides, or photosensitive initiators can be used.
Foaming agents can be added for the fabrication of wires, which require low dielectric constant and low dielectric loss tangent, such as communication cables, coaxial cables for computers, and highfrequency cables. Examples of foaming agents are sodium bicarbonate, ammonium bicarbonate and nitroso compounds. Especially, when dinitrosopentamethylenetetramine is used, foaming aids can be added that accelerate the decomposition and reduce the decomposition temperature.
This is achieved, for example, with salicylic acid, or with urea. Various chlorine and bromine flame retardants can be used as halogen-based flame retardants, e. The wire coating material can be coated on a conductor by coextruding the conductor and the molten material in an extrusion molding machine.
The compound is provided in the form of pellets. However, since the cyclic olefin polymer composition has a higher in glass transition temperature than PE, the cylinder temperature of the extruder must be set to a somewhat higher temperature than used in the conventional method. When the material is dissolved in an organic solvent and provided as a varnish, the varnish can be directly coated on the conductor. These methods can be optionally selected according to the thickness of the coating material and other desired properties. More recent developments are the preparation using sol-gel technology, and ROMP polymerization.
The various issues are reviewed in the literature Monolithic materials were introduced in separation science in the late s. There is a perpetual progress in this topic The suspension polymerization of norbornene-2,3-dicarboxylic anhydride in dichloromethane using a molybdenum-based initiator results in living, linear polymer chains with the active initiator at the polymer chain end.
The solubility of the poly norbornene2,3-dicarboxylic anhydride is dependent on the chain length.
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Oligomers with a degree of polymerization up to are soluble, whereas higher oligomers are insoluble. Thus, by adjusting an appropriate degree of polymerization, a precipitation type polymerization can be achieved.
In the second stage a crosslinking agent, e. A polymer is formed where the linear oligomer chains are fixed at the crosslinked matrix as pendent groups. Metathesis Polymers 31 In the last stage of polymerization the products are endcapped with ferrocenealdehyde or benzaldehyde in order to remove the molybdenum catalyst from the material The actual removal of catalyst occurs by a treatment with aqueous sodium hydroxide, which is followed by a treatment with hydrochloric acid.
Thereby the anhydride functionalities are hydrolyzed The materials were tested as supports for SPE techniques. Excellent recoveries are observed, exceeding silica-based SPE materials The supports were also investigated for their retention behavior for phenols, alcohols, carboxylic acids, aldehydes, ketones, esters, chloroalkenes, and polycyclic aromatic hydrocarbons In the same way, dipyridyl amide-functionalized supports suitable for the SPE of metal ions from aqueous solutions can be prepared. The resins are synthesized via the copolymerization of the functional monomer eiiifo-norborneneyl-N,N-dipyridyl carboxylic amide with a molybdenum-based catalyst Essentially no loss of performance was observed after extensive use over more than twenty cycles.
After exposure to air for at least 2 months, a change in color from bright white to yellow was observed. However, this change in color did not influence the characteristic properties of the resins. Separations of enantiomers can be achieved by chiral chromatography. Even, when the enantioselective synthesis of drugs and pharmaceuticals is possible, a major part of chiral compounds is still produced as a racemate and needs to be separated into the enantiomers by chiral high performance liquid chromatography. The separation of dinitrobenzoylphenylalanine can be achieved on a poly N- norbornenecarboxyl -L-phenylalanine ethylester grafted to Nucleosil Norbornene was functionalized with cyclodextrins and surface grafted onto silica-based supports using ROMP Materials prepared by the ROMP technique find use in monolithic capillary columns 45,46 , and monolithic membrane discs Traditionally, the stationary phase is packed in form of particles into the column.
In the present context, crosslinked, functionalized organic polymers can find application as monolithic stationary phase. In the case of capillary columns, in the initial step of preparation the surface is modified with bicyclo[2. This acts as an anchor for subsequent ROMP polymerization. Some functional monomers used for monolith grafting are shown in Figure 1. For example, poly norbornene is produced in quantities of around 5 k t a " 1 , under the tradename of Norsorex Examples for commercially available grades and tradenames are shown in Table 1.
Tradenames appearing in the references are shown in Table 1. Metathesis Polymers 33 Table 1. Dicyclopentadiene 23 Viron Toyo Boseki K.
For poly norbornene n o special h a z a r d s are reported. O n h a n d l i n g , the usual precautions should be applied. References 1. Eleuterio, Verfahren zur Polymerisation cyclischer, insbesondere mono-, bi-, oder tricyclischer Olefine, DE Patent , assigned to E. Chauvin, Catalysis of olefin transformations by tungsten complexes. II telomerization of cyclic olefins in the presence of acyclic olefins, Makromol.
Grubbs, The olefin metathesis reaction, Prog. Feast, E. Khosravi, and T. Obuchi, M. Tokoro, T.
Suzuki, H. Tanisho, and K. Otoi, Thermoplastic dicyclopentadiene-base open-ring polymers, hydrogenated derivatives thereof, and processes for the preparation of both, US Patent , assigned to Nippon Zeon Co. Tokyo, JP , January 28, Janiak and PG.
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