Ladder poly polymer types

Figure 2-7. Ordered networks. 0, Adamantane as an example of a cage polymer (type 0) I, Cyclized and dehydrogenated l,2-poly(butadiene) as an example of a ladder or double-strand polymer (type 1) 2, graphite as a layer or parquet polymer (type 2). ( ) Carbon-to-hydrogen bonds (— and =) carbon-to-carbon bonds.

Figure 9-1. Materials overview a few sclcclcd conjugated polymers and Ihcir properties have been compiled and ihe following abbreviations arc used DO-PPP...Poly(2-decyloxy-l,4-phcnylcnc), EHO-PPP...Poly(2-(2 -elhylliexyloxy)-l,4-phcnylenc), CN-PPP... Poly(2-(6 -cyano-6 -incthyl-licplyloxy)-l,4-phcnylene), m-LPPP... methyl-substituted ladder-type Poly( 1,4-phenylcne), and PLQY=phololuinincs-ecncc quanluni yield.

Ladder-Type Oligo- and Poly(pora-phenylene)s Polymers... 

In 1993, Scherf and Chmil described the first synthesis of a ladder-type poly(pflra-phenylene-czs-vinylene) (116) [138]. On the one hand, ladder polymer 116 represents, a planar poly(phenylene) containing additional vinylene bridges on the other hand, it is a poly(phenylenevinylene) with aryl-aryl linkages in the polymeric main chain. The target macromolecules, as fully aromatic ladder polymers, are composed of all-carbon six-membered rings in the double-stranded main chain (an example of angularly annelated poly(acene)s). 

XH Yang, D Neher, U Scherf, SA Bagnich, and H Bassler, Polymer electrophorescent devices utilizing a ladder-type poly(para-phenylene) host, J. Appl. Phys., 93 4413 -419, 2003. 

The speeifieation of the type of structure in a polymer is shown by an italicized prefix "ladder- or "spiro- preceding poly . 

Polymerization of multimethacrylate from poly(vinyl alcohol) leads to polymers with long ladder-type blocks according to the reaction ... 

Production of materials in which the daughter polymer and the template together form a final product seems to be the most promising application of template polymerization because the template synthesis of polymers requiring further separation of the product from the template is not acceptable for industry at the present stage. Possible method of production of commonly known polymers by template polymerization can be based on a template covalently bonded to a support and used as a stationary phase in columns. Preparation of such columns with isotactic poly(methyl methacrylate) covalently bonded to the microparticulate silica was suggested by Schomaker. The template process can be applied in order to produce a set of new materials having ladder-type structure, properties of which are not yet well known. A similar method can be applied to synthesis of copolymers with unconventional structure. 

A similar method of hydrolysis was described for poly( vinyl alcohol) used as a template. In this case, T was -CH2-CH- and, after hydrolysis, poly(vinyl alcohol) and polyacrylic or polymethacrylic acid were obtained. The hydrolyzed product gives the color reaction with I2 in the presence of H3BO3 - specific to poly(vinyl alcohol). The second product of hydrolysis, after esterification by diazomethane, was identified as polyfmethyl methacrylate) by NMR and IR spectrometry. Hydrolysis was also applied in the case of ladder-type polymers obtained by polymerization of mutliallyl monomers. The polymerization should result in polymer consisting, at least partly, ladder-type blocks ... 

An alternative polymerization mechanism and polymer architecture has been proposed by Kirchhoff [1, 2, 3], Tan and Arnold [77], By this mechanism, polybenzocyclobutenes which do not contain reactive sites of unsaturation are proposed to polymerize by the 1,4 addition of the o-quinodimethane intermediates to give a substantially linear poly(o-xylylene) structure. Since the monomers all contain at least two benzocyclobutene units the net result of this reaction will to a first approximation be a ladder type polymer as shown in Fig. 17. The formation of a true ladder polymer however would require that all... 

Fig. 17. Proposed polymerization of a bisbenzocyclobutene to give a ladder type poly(o-xylylene) polymer 30...

Polymers containing cyclophane-type moieties were also prepared for their unique functionalities and potential applications. Thus, isotactic poly(para-phenylene) ladder polymer (56) was prepared from the corresponding bromide and borate (55) in enantiomerically pure forms and subjected to the CD spectral measurement [62],... 

An electrophilic substitution reaction has been used for the key ladderforming step in the synthesis of soluble ladder-type poly(phenylene)s [51-53]. These aromatic polymers have a ribbon-like rigid, planar structure. They are of interest because of their optical and electronic properties [51,54,55]. The preparation of these polymers was accomplished by two basic steps. The first step was the construction of a substituted poly(p-phenylene) backbone. The ladder structure was obtained by a subsequent intramolecular electrophilic ring closure reaction. For example, the syn-... 

The amidic bonds within amino acids can be also used to effect the organization of polymers into superstructures (Fig. 10). Thus, the formation of artificial helices on the basis of assembling polymers has been described by use of poly(acetylenes) bearing pendant L-valine side-chains. [71,72] Two effects are important for the association of these ladder-type polymers into double-stranded helices (a) the reduction of conformational freedom by the poly(acetylene) chain with respect to a conventional alkyl-chain and (b) the selective association of the L-valine residues by specific hydrogen bonding. An AFM image of the associates on a fiat surface demonstrates the presence of a string-pearl structure reminiscent of natural DNA. 

Polysiloxanes. The initial reports of the utility of polysiloxanes for lithographic applications spurred several research groups to further investigate this class of materials. The problem of low Tg was addressed by preparing chloromethylated poly(diphenylsiloxane) 16, 17). More recently, poly(sil-sesquioxanes) 18, 19) have been reported as sensitive, negative, e-beam, ion-beam, and UV resists. These soluble, ladder -type polymers prepared by the hydrolysis of substituted chloro- and alkoxysilanes are high-Tg materials (150 °C) with high silicon contents. 

The use of Diels-Alder-type cycloaddition reactions is the most intensively investigated cycloaddition approach to the design of ladder polymers in a concerted process. Another methodology was published by Tsuda and coworkers [52, 53, 54]. They developed a nickel (0)-catalyzed [2 + 2 -l- 2] cycloaddition copolymerization of cyclic diynes 38 with heterocumulenes (like carbon dioxide or isocyanates 39). The soluble ladder-type products - poly(2-pyrone)s and poly(2-pyridone)s 40 - possess molecular weights M of up to 60000, corresponding to a Dp > 200. Unfortunately, the products formed were contaminated by nickel salts originating from the catalyst used Ni(COD)2. 

The above examples of a stepwise synthesis of a ladder polymer involve the formation of single-stranded polymers via polymerization of suitable monomers to functionalized precursors. These consist of substituted poly(ethylene)- or (polyacetelyne)-type macromolecules, from which attempts are made to carry out a defined polymer-analogous cyclization reaction. 

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