Poly polycondensation with

The reaction of ACPC with linear aliphatic amines has been investigated in a number of Ueda s papers [17,35,36]. Thus, ACPC was used for a interfacia] polycondensation with hexamethylene diamine at room temperature [17] yielding poly(amide)s. The polymeric material formed carried one azo group per repeating unit and exhibited a high thermal reactivity. By addition of styrene and methyl methacrylate to the MAI and heating, the respective block copolymers were formed. 

Diamine 108 led to 95% ee for the alkylation of l,3-diphenyl-2-propenyl acetate with 90% yield. By polycondensation with a diacid chloride or polyaddition with a diisocyanate, this ligand led, respectively, to an insoluble poly(amide) 109 or poly(urea) 110 with excellent yields. Poly(amide) 109 gave a better ee (80%) than poly(urea) 110 (38%), albeit with a lower conversion (respectively, 38 and 72%), when they were used as palladium hgands... 

Weight average molecular weights of poly(HAMCL) with saturated or unsaturated pendent groups are relatively low, compared to Mw s of poly(HASCL), and in the range of 60,000 to 360,000 g mol as depicted in Table 2 [4,30,35,36]. Also for the poly(HAMCL) copolymers, the molecular weight distributions are unimodal. Their polydispersities are in the range of 1.6-2.4, which is narrower than the polydispersity of poly(3HB-co-3HV) copolymers, and close to the theoretical value of 2.0 for synthetic polycondensates such as chemically synthesized polyesters [54]. 

Polycondensation reactions were also carried out using a mixture of ethylene-diamine and adipic acid (55). IR techniques again were usai to confirm the polymer composition. The results are summarized on Table 9. The chemistry of poly(ethylene terephthalate) mechanical polycondensation with diamines proceeds as follows ... 

In polycondensation systems, a poly(dimethylsiloxane) with hydroxy end-groups at either end and a viscosity of 10- to 10 mPa s is crosslinked with tetraalkoxysilanes, e.g. tetraethoxysilane, in the presence of a condensation-accelerating tin compound e.g. dibutyltin dilaurate. Since this hardening, in contrast with single component products, is not dependent upon water diffusion through the hardening mass, thick layers of such rubber systems can be crosslinked quickly and homogeneously. 

Okamoto [289] synthesized identical macromonomers that had been poly-condensed with prepolycarbonates, obtaining polycarbonatc-gra/f- PMMA. The PMMA grafting chain brings transparency and toughness to polycarbonate matrices. Other authors used this technique to synthesize dihydroxy PS macromonomers, used in the synthesis of polyester by polycondensation with terephtalic acid and butylene glycol. 

Furthermore, the group of Deimede [338-340] performed the synthesis of a-dicarboxy end-functionalized PS macromonomers by using ATRP (Scheme 72). Further polycondensation with dihydroxy end functionalized polyethylene oxide) led to alternating branched PS/poly(ethylene oxide) poly(macromonomers) (Scheme 72). These novel amphiphilic compounds afforded the formation of stable micelles, especially in THF or dioxane. 

CBZ-PMDA), carbazole-1,4,5,8-naphthalene tetracar-boxylic dianhydride (CBZ-NTDA) and carbazole-benzophenone tetracarboxyl dianhydride (CBZ-BTDA) were synthesized by a similar method. Poly(N-vinyl-carbazole)-anhydride co-polycondensates such as PNVC-PhAn, PNVC-TMA, PNVC-PMDA, PNVC-NTDA and PNVC-BTDA were also prepared. Thermal stability characteristics of the various polycondensates have been compared in Table 16.18 and it was observed that (i) the initial decomposition temperature and the overall stability of a co-polycondensate of either CBZ or PNVC depends upon the anhydride moiety in the order of NDTA > BTDA > PMDA >TMA > PhAn (ii) initial decomposition temperature and the overall stability of a co-polycondensate with a fixed anhydride, vary in the order PNVC > CBZ and (iii) polycondensation of PNVC by anhydrides improves the thermal stability of the base polymer. It is suggested that the incorporation of thermally stable moieties, cross-links and rigidity is the main reason for enhanced initial decomposition temperature as well as overall thermal stability of these co-polycondensates. Table 16.19 gives the isothermal degradation stability of pairs of polycondensates and data confirm the high thermal stability... 

The Introduction of the styrylketone group into a polymer molecule as lateral substituent has been realized by the condensation of poly(vlnylacetophenone) with benzaldehyde giving poly-(vlnyl-trans-benzalacetophenone). Direct incorporation of the clnnamoyl photosensitive group into a polymeric chain was obtained by polycondensation of specific derivatives. Photo-cross-linkable polymers obtained by polycondensation techniques provide systems with varying thermal and solubility properties. 

Figure 11.3 shows an example of polycondensation with a Grignard reaction. Treating a solution of 2-bromthienyl-3-alkyl-5-magnesiumbromide in the presence of [1,3-bis (diphenylphosphino)propane]nickel(ll)-chloride as a catalyst leads to fonnation of poly-3-alkylthiophene and magnesium bromide (Kumada-McCullough process). ... 

Preparations of poly-p-phenyleneterephthalamide by polycondensations with N-silylated diamine proceed more rapidly than with the parent diamine.In addition, the products have higher molecular weights than a similar commercial material made from the parent diamine and sold under the trade name of Kevlar. 

From these monomers, poly(phenylene ether)s can be formed by the aromatic nucleophilic substitution polycondensation with dihydroxy-monomers in the presence of potassium carbonate. 

Poly(amide)s can be formed by a direct polycondensation with either aromatic or aliphatic dicarboxylic acids. The polymers can be reinforced and thermally stabilized with silicon carbide. These poly(amide)s emit green or blue fluorescence in dilute A-methyl-2-pyrrolidinone solution and in the solid state [77]. 

A poly(inude-urea) can be synthesized in a two-stage procedure including the condensation reaction between 2-anunophenol, 2-amino thiophenol, or m-phenylenedianune and 3,5-diaminobenzoic acid in the presence of poly(phosphoric acid). Then this product is refluxed in glacial acetic acid with trimellitic anhydride to get an aromatic poly(amide-imide) with ben-zazole hetero rings. From these products, poly(imide-urea)s can be obtained by the direct polycondensation with aromatic diamines [15]. 

Copolyesters have also been synthesized by interfacial polycondensation, with aromatic-aliphatic structures. The introduction of an aliphatic diol into aromatic polyester was found to influence glass-transition temperature, softening point, and chemical and thermal stability. Trans-gauche rotational isomers in poly(ethylene terephthalate) in fibre form have also been produced," as have lactide-glycolide copolyesters. "... 

Triblockcopolymers derived from a central block of PES and two wings of poly(phenylene oxide) were also reported [57]. For this purpose oligo(ether sulfone)s were synthesized with an excess of DFDPS, so that two C-F endgroups were obtained (37). These oligomers were then polycondensed with poly(phenylene oxide)s having one trimethylsiloxy endgroup whereby CsF served as catalyst (38). Multiblock copolymers... 

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