Thermally-crosslinking polymers

Fig. 1. Schematic representation of different types of functionalized polymers guest-host system(a), side-chain polymer (b), main-chain polymer (c), photo-and thermally crosslinking polymer...

Literature articles, which report the formation and evaluation of difunctional cyanoacrylate monomers, have been published. The preparation of the difunctional monomers required an alternative synthetic method than the standard Knoevenagel reaction for the monofunctional monomers, because the crosslinked polymer thermally decomposes before it can revert back to the free monomer. The earliest report for the preparation of a difunctional cyanoacrylate monomer involved a reverse Diels-Alder reaction of a dicyanoacrylate precursor [16,17]. Later reports described a transesterification with a dicyanoacrylic acid [18] or their formation from the oxidation of a diphenylselenide precursor, seen in Eq. 3 for the dicyanoacrylate ester of butanediol, 7 [6]. 

Thermal expansion — as elasticity — depends directly upon the strength of the intermolecular forces in the material. Strongly bonded materials usually expand little when heated, whereas the expansion of weak materials may be a hundred times as large. This general trend is confirmed by Table 5.1. The coefficient of thermal expansion a was found to be lower in the crosslinked polymers and higher in the less crosslinked or thermoplastic materials as observed by Nielsen [1], In addition, Table 5.1 presents the Young s moduli E of the polymers at ambient temperatures as well as the products a2E. The values of oc2E are all close to 13.1 Pa K 2 with a coefficient of variation of 1.6%. 

Synthesis of comb (regular graft) copolymers having a PDMS backbone and polyethylene oxide) teeth was reported 344). These copolymers were obtained by the reaction of poly(hydrogen,methyl)siloxane and monohydroxy-terminated polyethylene oxide) in benzene or toluene solution using triethylamine as catalyst. All the polymers obtained were reported to be liquids at room temperature. The copolymers were then thermally crosslinked at 150 °C. Conductivities of the lithium salts of the copolymers and the networks were determined. 

A new crosslinkable polymer was synthesized by the SBP-catalyzed polymerization of cardanol. When HRP was used as catalyst for the cardanol polymerization, the reaction took place in the presence of a redox mediator (phe-nothiazine derivative) to give the polymer. Fe-salen efficiently catalyzed the polymerization of cardanol in organic solvents (Scheme 29). " The polymerization proceeded in 1,4-dioxane to give the soluble polymer with molecular weight of several thousands in good yields. The curing of the polymer took place in the presence of cobalt naphthenate catalyst at room temperature or thermal treatment (150°C for 30 min) to form yellowish transparent films ( artificial urushi ... 

By the addition of glass fibers, textile fibers, or chopped fabrics to crosslinkable polymers molding materials are produced with increased tensile strength, stiffness, and thermal stability compared to the filler-free polymers. The so-called reinforcing fillers, like carbon black, have good adhesion to the matrix due to their nonpolar structure and their characteristic geometry. 

Various a-methylenemacrolides were enzymatically polymerized to polyesters having polymerizable methacrylic methylene groups in the main chain (Fig. 3, left). The free-radical polymerization of these materials produced crosslinked polymer gels [10, 12]. A different chemoenzymatic approach to crosslinked polymers was recently introduced by van der Meulen et al. for novel biomedical materials [11]. Unsaturated macrolactones like globalide and ambrettolide were polymerized by enzymatic ROP. The clear advantage of the enzymatic process is that polymerizations of macrolactones occur very fast as compared to the chemically catalyzed reactions [13]. Thermal crosslinking of the unsaturated polymers in the melt yielded insoluble and fully amorphous materials (Fig. 3, right). 

One resin based on the BTDA/ODA backbone and 2-aminobiphenylene as an endcapper was thought to be such a resin (126). High quality laminates could be fabricated, but the Tg of the crosslinked polymer was lower than expected and therefore thermal oxidative stability was poor. The chemical structure of this thermosetting polyimide is given in Fig. 42. 

An investigation of the thermal and thermooxidative stability of crosslinked polymers obtained from BPA/DC and BPA/DC compositions with BPA/ECH epoxide resin or epoxynovolak resin has demonstrated that the epoxy resin decreased the thermal stability of BPA/DC based non-modified polycyanurate [71]. The systems with epoxynovolak resin behave somehow better. 

When 8-hydroxyquinoline and derivatives of bis(8-hydroxy-quinoline) react with metal ions, coordination complexes and polymers are formed, respectively, which exhibit improved thermal stability. This paper reviews the reaction of first-row transition metal ions with such ligands and their effect on the stabilization of these organic molecules. For the polymers containing divalent Mn, Co, Ni, Cu, or Zn the decomposition temperature is related to the periodic properties of the metal as well as the composition of the ligand to which the metal is coordinated. Trivalent chromium produces a crosslinked polymer when it reacts with bis(8-hydroxy-5-quinolyl)methane, and the thermogram for this polymer is also reported. 

The formation of tri- and especially tetrasilanes which are already branched (tertiary Si-units) as the first reaction products (described elsewhere [4]) suggests the appearance of intermediate silylene species which could enter in insertion reactions of Si-Si as well as Si-Cl bonds. The tri- and tetrasilanes undergo thermal crosslinking reactions at reaction temperatures of 165-250 °C. In addition dehydrochlorination reactions initiated by acid H-abstraction of methyl groups cause the formation of carbosilane (methylene) units in the polymer framework. Table 1 shows the gross compositions of poly(methylchlorosilanes) which are determined by the reaction temperature. 

Separation of VOCs is usually performed by GC, because it allows efficient separation of compounds. Nowadays, GC capillary columns are high performance and thermally resistant. Separation of VOCs is done by columns of high thermal stability containing effectively crosslinked polymer that is chemically bonded to the surface of the capillary. 

Oligomer 163 represents a stabilizer having PA chain with pendant phenolic moiety [31], Pendant hindered piperidine or piperazine moieties were attached to oligomeric stabilizers having polysulfonamide, polyurea (e.g. 164), or PA (e.g. 165) unis [213]. Polyhydrazide 166 was tested as HD AO and copper deactivator in PP [214]. Poly (nitrophenylene-carbazide disulfide) 167 was prepared for thermal stabilization of PVC. Phosphorus containing crosslinkable polymers having polyamide, polyimide and polyurea chains were prepared for flame and heat resistant applications [215]. 

Previous work pursued the model analytically, for a linearly elastic [5] (or, later, non-linearly elastic [6]) material with constant thermal properties. The analytical model explained several measured fracture properties of thermoplastics the magnitude of impact fracture toughness and its dependence on impact speed [7] and the absolute magnitude of resistance to rapid crack propagation [8]. Recent results have shown that the impact fracture properties of some amorphous and crosslinked polymers show the same rate dependence [11],... 

The compounds cured thermally to form crosslinked polymers with 343 °C stability in air. The curing characteristics of oligoimides end-capped with aminobenzocyclo-butene were also described [93]. 

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