Polymers with functional groups

As mentioned before, problems with monomers with functionalities with acid hydrogen have been encountered with some types of catalysts. Now, the direct incorporation of polar functional groups along the backbone of linear polymers made via ROMP is possible due to the development of functional group-tolerant late transition metal olefin metathesis catalysts (10). 

The ROMP of alcohol, ketone, halogen, and acetate substituted cyclooctenes with a ruthenium olefin metathesis catalyst has been reported (31). 

The interest of functional polymers originates among others in the fact that for example, the hydroxyl group imparts barrier properties of the polymer. 

The asymmetry of the substituted cyclooctene allows for head-to-head (HH), head-to-tail (HT), and tail-to-tail (TT) coupling, yielding a polymer with regio-random placement of the functional groups. 

A similar problem was encountered by the ROMP of a borane substituted cyclooctene with an early transition metal catalyst followed by oxidation to yield an alcohol-functionalized linear polymer (32). 

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Postelnek,W., Colemann, L. E., and Lovelace, A. M. Fluorine-Containing Polymers. I. Fluorinated Vinyl Polymers with Functional Groups, Condensation Polymers, and Styrene Polymers. Vol. 1, pp. 75— 113. 

I. Fiuorinated Vinyl Polymers with Functional Groups, Condensation Polymers, and Styrene Polymers. Vol. 1, pp. 75-113. 

Fluorinated polymers, especially polytetrafluoroethylene (PTFE) and copolymers of tetrafluoroethylene (TFE) with hexafluoropropylene (HFP) and perfluorinated alkyl vinyl ethers (PFAVE) as well as other fluorine-containing polymers are well known as materials with unique inertness. However, fluorinated polymers with functional groups are of much more interest because they combine the merits of pefluorinated materials and functional polymers (the terms functional monomer/ polymer will be used in this chapter to mean monomer/polymer containing functional groups, respectively). Such materials can be used, e.g., as ion exchange membranes for chlorine-alkali and fuel cells, gas separation membranes, solid polymeric superacid catalysts and polymeric reagents for various organic reactions, and chemical sensors. Of course, fully fluorinated materials are exceptionally inert, but at the same time are the most complicated to produce. 

Fluori iialed Polymers with Functional Groups... 

It is also possible to prepare polymers with functional groups by partial saponification of polyvinyl esters to give OH groups or polyacrylic esters or Polyacrylonitrile to give COOH groups. Polymer with such functional groups at the chain ends are prepared... 

The key advantages of the anionic ROP method are that with suitable catalysts, polymers with controlled microstructure can be prepared, and also that polymers with functional groups can be formed. (Although prior to the time frame of this edition, ROPs of [(I I3C=C)SiPh]4, [(MeO)SiPh]4, and [(NC)SiPh]4 have also been reported, few experimental details or analytical data were given.)97... 

Produced diallyllsilazanes and polymers based on them were used for the modification of the properties of some industrial polymer composites based on polymers with functional groups. 

The theory of chromatography of linear and cyclic polymers with functional groups has also been developed. A linear in-pore partition function Q 1) was created for polymeras with one specific functional group a. Q 1) can be expressed by... 

Cyclic ketene acetals, which have utility as co-polymers with functional groups capable of cross-linking, etc., have been prepared by the elimination of HX from 2-halomethyl-l,3-dioxolanes. Milder conditions are used under phase-transfer conditions, compared with traditional procedures, which require a strong base and high temperatures. Solid liquid elimination reactions frequently use potassium f-butoxide [27], but acceptable yields have been achieved with potassium hydroxide and without loss of any chiral centres. The added dimension of sonication reduces reaction times and improves the yields [28, 29]. Microwave irradiation has also been used in the synthesis of methyleneacetals and dithioacetals [30] and yields are superior to those obtained with sonofication. 

Fluorinated Polymers with Functional Groups Synthesis and Applications. Langmuir-Blodgett Films from Functional Fluoropolymers... 

Grafting from involves a polymer with functional groups that initiate polymerization of... 

Crosslinked polymers with functional groups have recently been used even more frequently as reagents for the synthesis of low-molecular-weight organic compounds since they are easily separated after conversion and sometimes can easily be regenerated. The immobilization of enzymes by attaching them to crosslinked polymers should also be mentioned. This technique has already found industrial applications. 

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