Poly drawbacks

A protonic acid derived from a suitable or desired anion would seem to be an ideal initiator, especially if the desired end product is a poly(tetramethylene oxide) glycol. There are, however, a number of drawbacks. The protonated THF, ie, the secondary oxonium ion, is less reactive than the propagating tertiary oxonium ion. This results in a slow initiation process. Also, in the case of several of the readily available acids, eg, CF SO H, FSO H, HCIO4, and H2SO4, there is an ion—ester equiUbrium with the counterion, which further reduces the concentration of the much more reactive ionic species. The reaction is illustrated for CF SO counterion as follows ... 

The earliest study describing vulcanised polymers of esters of acryUc acid was carried out in Germany by Rohm (2) before World War I. The first commercial acryUc elastomers were produced in the United States in the 1940s (3—5). They were homopolymers and copolymers of ethyl acrylate and other alkyl acrylates, with a preference for poly(ethyl acrylate) [9003-32-17, due to its superior balance of properties. The main drawback of these products was the vulcanisation. The fully saturated chemical stmcture of the polymeric backbone in fact is inactive toward the classical accelerators and curing systems. As a consequence they requited the use of aggressive and not versatile compounds such as strong bases, eg, sodium metasiUcate pentahydrate. To overcome this limitation, monomers containing a reactive moiety were incorporated in the polymer backbone by copolymerisation with the usual alkyl acrylates. 

One of the earliest observations of high eonductivity in sueh a material was in a form of poly(acetylene) by a Japanese team (Shirakawa and Ikeda 1971). Perhaps one should date the pursuit of semieondueting polymer deviees from that experiment. It soon became clear that conjugated polymers had a severe drawback most of them are extremely stable against potential solvents they cannot be forced... 

Tetrahydrofuran (THF) is usually the solvent of choice for poly (acrylates). It is an excellent thermodynamic as well as kinetic solvent, its only drawback being its volatility and flammability. 

The drawback of the described adsorbents is the leakage of the bonded phase that may occur after the change of eluent or temperature of operation when the equilibrium of the polymer adsorption is disturbed. In order to prepare a more stable support Dulout et al. [31] introduced the treatment of porous silica with PEO, poly-lV-vinylpyrrolidone or polyvinylalcohol solution followed by a second treatment with an aqueous solution of a protein whose molecular weight was lower than that of the proteins to be separated. Possibly, displacement of the weakly adsorbed coils by the stronger interacting proteins produce an additional shrouding of the polymer-coated supports. After the weakly adsorbed portion was replaced, the stability of the mixed adsorption layer was higher. 

These carbonyl chloride-activated carriers are unstable on storage, so ligand coupling to them has to be undertaken immediately after chemisorption of the copolymer. To overcome this drawback, more stable activated carriers have been synthesized by treating aminopropyl-silicas with poly(p-nitrophenyl acrylate) and acetic anhydride. 

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. 

In solution polymerization, monomers mix and react while dissolved in a suitable solvent or a liquid monomer under high pressure (as in the case of the manufacture of polypropylene). The solvent dilutes the monomers which helps control the polymerization rate through concentration effects. The solvent also acts as a heat sink and heat transfer agent which helps cool the locale in which polymerization occurs. A drawback to solution processes is that the solvent can sometimes be incorporated into the growing chain if it participates in a chain transfer reaction. Polymer engineers optimize the solvent to avoid this effect. An example of a polymer made via solution polymerization is poly(tetrafluoroethylene), which is better knoivn by its trade name Teflon . This commonly used commercial polymer utilizes water as the solvent during the polymerization process,... 

As mentioned previously, the main drawbacks of the thermal route to poly-borylborazine are (1) the presence of both direct intercyclic bonds and three-atom bridges between the rings, and (2) a difficulty in controlling the polycondensation rate. One solution we investigated to address these drawbacks is a route based on the room temperature reaction of /i-chloroborazine with trialkylaminoborane.31 32 We used 2-methylamino-4,6-dichloroborazine instead of 2,4,6-trichloroborazine to prepare a two-point polymer (scheme 4), which is theoretically less cross-linked. 

The drawbacks can be overcome by employing a block copolymer composed of poly(ethylene-a/f-propylene), PEP, and polydimethylsiloxane... 

At present, a wide range of solid substrates are available for protein immobilization. According to the protein attachment strategies, namely, adsorption, affinity binding, and covalent binding, all these substrates can be separated into three main parts. Surfaces like ploy(vinylidene fluoride) (PVDF), poly(dimethylsiloxane) (PDMS), nitrocellulose, polystyrene, and poly-1-lysine coated glass can adsorb proteins by electrostatic or hydrophobic forces. A potential drawback of such substrates is the difficulty... 

The major drawback of poly(p-xylylene) is that it reverts to a monomer when thin films are heated above ca. 400°C and it cracks when the films are annealed at 300-350°C in nitrogen. During module assembly the chip-joining (soldering)... 

Before fluorination, the dielectric constant ofpoly(bisbenzocyclobutene) was 2.8, and this value was reduced to 2.1 after plasma treatment. No data were reported in the paper on characterization of structure or properties, except for the dielectric constant of the modified poly(bisbenzocyclobutene). The authors did report that the thermal stability offluorinatedpoly(vinylidenefluoride) was inferior to the original poly(vinylidenefluoride) when treated in a similar way. One of the probable reasons for the low thermal stability is that the NF3 plasma degraded the polymer. According to their results, the thickness of fluorinated poly(bisbenzo-cyclobutene) was reduced by 30%. The same phenomenon was observed for other hydrocarbon polymers subjected to the NF3 plasma process. A remaining question is whether plasma treatment can modify more than a thin surface layer of the cured polymer Additionally, one of the side products generated was hydrogen fluoride, which is a serious drawback to this approach. 

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