Thermal polymerization reactions

The solution polymerization process for hexachlorocyclophosphazene to poly-dichlorophosphazene is an interesting and attractive alternative to the classic bulk thermal polymerization reaction of this trimer. 

ESR (electron spin resonance) and optical absorption spectroscopy at low temperatures were used to analyse the individual reaction steps of the optical and thermal polymerization reactions and their kinetics. The reaction steps are the photoinitiation, the chain propagation and chain termination reactions. 

A direct measure of the optical absorption coefficient a is the optical density OD defined by OD = log Iq/I = 0,434od (Iq and I are the incident and the transmitted light intensities and d is the thickness of the crystal). Weak polymer absorption in the range from 600 to 400 nm is present in the original monomer crystals due to weak thermal polymerization reactions. The absorption of the linear polymer molecules (which are homogeneously distributed within the partially polymerized monomer diacetylene crystals) increase during UV-irradiation at room temperature due to photopolymerization reactions. In contrast to the monomer absorption, the polymer... 

The reaction mechanisms of this extraordinary solid state reaction has strongly attracted the interest of the polymer chemists from the very beginning. Valuable information on several aspects of the thermal polymerization reaction mechanisms, have been obtained from X-ray structural and physico-chemical investigations, discussed by Wegner Baughman and Chance . However, the identifi-... 

In contrast to the thermal addition reactions (following the photodimerization) the high activation energy of the purely thermal polymerization reaction (without... 

In this article it has been shown, that the low temperature photopolymerization reaction of diacetylene crystals is a highly complex reaction with a manifold of different reaction intermediates. Moreover, the diacetylene crystals represent a class of material which play a unique role within the usual polymerization reactions conventionally performed in the fluid phase. The spectroscopic interest of this contribution has been focussed mainly on the electronic properties of the different intermediates, such as butatriene or acetylene chain structure, diradical or carbene electron spin distributions and spin multiplicities. The elementary chemical reactions within all the individual steps of the polymerization reaction have been successfully investigated by the methods of solid state spectroscopy. Moreover we have been able to analyze the physical and chemical primary and secondary processes of the photochemical and thermal polymerization reaction in diacetylene crystals. This success has been largely due to the stability of the intermediates at low temperatures and to the high informational yield of optical and ESR spectroscopy in crystalline systems. 

Fullerene-styrene copolymers have been prepared in radical initiated and thermal polymerization reactions [148-151]. In radical copolymerizations of Cgg and styrene, copolymers with Cgg contents up to 50% (wt/wt) can be obtained [150]. Electronic absorption spectra of the copolymers are very different from that of monomeric C o (Fig. 36). The absorptivities per unit weight concentration of the copolymers j increase with increasing C q contents in the copolymers in a nearly linear relationship (Fig. 37). Fluorescence spectra of the Cgg-styrene copolymers, blue-shifted from the spectrum of monomeric Cgo, are dependent on excitation wavelengths in a systematic fashion [149]. Interestingly, the observed absorption and fluorescence spectral profiles of CgQ-styrene and Cyg-styrene copolymers are very similar, even though the spectra of monomeric CgQ and C70 are very different. The absorption and fluorescence spectra of the fullerene-styrene copolymers are also similar to those of the pendant Cgg-poly-styrene polymer (19) prepared in a Friedel-Crafts type reaction [150,156]. 

While these thermal polymerization reactions could be carried out by equimolar melts, it was found that such conditions were difficult to control on larger scales and the use of high boiling solvents gave more consistent results. The use of solvents such as mesitylene and 1,2-dichlorobenzene gave quantitative yields after 16 h, but the products isolated indicated significant amounts of impurities and defects. The use of the lower boiling xylene resulted in reduced conversion yields. 

Synthetic Fiber and Plastics Industries. In the synthetic fibers and plastics industries, the substrate itself serves as the solvent, and the whitener is not appHed from solutions as in textiles. Table 6 Hsts the types of FWAs used in the synthetic fibers and plastic industries. In the case of synthetic fibers, such as polyamide and polyester produced by the melt-spinning process, FWAs can be added at the start or during the course of polymerization or polycondensation. However, FWAs can also be powdered onto the polymer chips prior to spinning. The above types of appHcation place severe thermal and chemical demands on FWAs. They must not interfere with the polymerization reaction and must remain stable under spinning conditions. 

Polymerization. Thermal polymerization or curing of an ink film at elevated temperatures can foUow many different chemical paths. Condensation and cross-linking reactions may be accompHshed with or without the use of catalysts. However, this method of drying generally has not been widely used for printing inks, except those used for metal and glass decoration, and some clear coatings. 

Thermal polymerization is not as effective as catalytic polymerization but has the advantage that it can be used to polymerize saturated materials that caimot be induced to react by catalysts. The process consists of the vapor-phase cracking of, for example, propane and butane, followed by prolonged periods at high temperature (510—595°C) for the reactions to proceed to near completion. Olefins can also be conveniendy polymerized by means of an acid catalyst. Thus, the treated olefin-rich feed stream is contacted with a catalyst, such as sulfuric acid, copper pyrophosphate, or phosphoric acid, at 150—220°C and 1035—8275 kPa (150—1200 psi), depending on feedstock and product requirement. 

Poly(arylene vinylenes). The use of the soluble precursor route has been successful in the case of poly(arylene vinylenes), both those containing ben2enoid and heteroaromatic species as the aryl groups. The simplest member of this family is poly(p-phenylene vinylene) [26009-24-5] (PPV). High molecular weight PPV is prepared via a soluble precursor route (99—105). The method involves the synthesis of the bis-sulfonium salt from /)-dichloromethylbenzene, followed by a sodium hydroxide elimination polymerization reaction at 0°C to produce an aqueous solution of a polyelectrolyte precursor polymer (11). This polyelectrolyte is then processed into films, foams, and fibers, and converted to PPV thermally (eq. 8). 

Grafting reactions onto a polymer backbone with a polymeric initiator have recently been reported by Hazer [56-60]. Active polystyrene [56], active polymethyl methacrylate [57], or macroazoinitiator [58,59] was mixed with a biopolyester polyhydroxynonanaate [60] (PHN) or polybutadiene to be carried out by thermal grafting reactions. The grafting reactions of PHN with polymer radicals may proceed by H-abstraction from the tertier carbon atom in the same manner as free radical modification reactions of polypropylene or polyhy-droxybutyratevalerate [61,62]. 

Hazer [20,25] reported on the reaction of a po]y(eth-ylene g]ycol)-based azoester with methacryloyl chloride in the presence of (CH3CH2)3N. In this reaction double bonds were attached to the chain ends of the poly(ester) thus obtaining a macroinimer. Being used for the thermal polymerization of styrene, the material formed an insoluble gel [20]. Probably, both the C=C double bonds and the azo bonds reacted in the course of the thermal treatment. The macroninimer in a later work [25] was used for thermally polymerizing poly(butadiene) thus leading to poly(ethylene glycol-/ -butadiene) block copolymers. 

Polyaddition reactions based on isocyanate-terminated poly(ethylene glycol)s and subsequent block copolymerization with styrene monomer were utilized for the impregnation of wood [54]. Hazer [55] prepared block copolymers containing poly(ethylene adipate) and po-ly(peroxy carbamate) by an addition of the respective isocyanate-terminated prepolymers to polyazoesters. By both bulk and solution polymerization and subsequent thermal polymerization in the presence of a vinyl monomer, multiblock copolymers could be formed. 

Generation of radicals by redox reactions has also been applied for synthesizing block copolymers. As was mentioned in Section II. D. (see Scheme 23), Ce(IV) is able to form radical sites in hydroxyl-terminated compounds. Thus, Erim et al. [116] produced a hydroxyl-terminated poly(acrylamid) by thermal polymerization using 4,4-azobis(4-cyano pentanol). The polymer formed was in a second step treated with ceric (IV) ammonium nitrate, hence generating oxygen centered radicals capable of starting a second free radical polymeriza-... 

HPO group is sensitive to light, but stable to heat. Using this MAI, St was thermally polymerized at the first step, and then MMA was photopolymerized at the second step [12]. Block efficiency was 40-55% and the amount of PSt homopolymer decreased, while that of PMMA homopolymer increased, presumably due to chain transfer reaction. 

Dilatometer Basically it is a pyrometer equipped with instruments to study density as a function of temperature and/or time. It can measure the thermal expansion or contraction of solids or liquids. They also study polymerization reactions it can measure the contraction in volume of unsaturated compounds. It basically is a technique in which a dimension of a material under negligible load is measured as a function of temperature while it is subjected to a controlled temperature program. 

Polymeranalogous reactions considered above may be referred to as intramolecular condensation transformations since they are accompanied by elimination of low-molecular products. On the other hand, PCSs can be obtained via polymeranalogous transformations, principally intramolecular polymerization reactions . Thermal and chemical cyclization of poly(acrilonitrile) (PAN) is an example of processes of this type. It was demonstrated by a number of researchers216-225 that thermal transformations of PAN follow the scheme ... 

Consider alternative polymerization processes in solid state, inducing the polymerization reaction of N3P3CI6 thermally [40-42],photochemically [61, 67,68],y-radiolytically [66,210], using X-rays [74,75,90] or electron irra-... 

The problem of the thermally induced polymerization reaction of partially or completely substituted cyclophosphazenes has been considered in the past by several authors [355-357], and more recently by H. R. AUcock [358]. This is because of the ease of synthesizing these substrates, the possibihty of preparing structurally regulated poly(organophosphazenes), and the lack of any additional nucleophilic substitution processes on the poly(organophosphazenes) obtained by the ROP process of fully saturated trimers. 

Differential scanning calorimetry (DSC) experiments on the various dimeric carbocycles indicated that, depending on the length of the alkyl groups, thermal polymerization had occurred between 100 and 125°C as an abrupt, exothermic process. The narrow temperature range for each exotherm was suggestive of a chain reaction however, IR spectroscopy revealed the absence of acetylene functionalities in the polymerized material. Consequently, none of the substi-... 

Chemoenzymatic synthesis of alkyds (oil-based polyester resins) was demonstrated. PPL-catalyzed transesterification of triglycerides with an excess of 1,4-cyclohexanedimethanol mainly produced 2-monoglycerides, followed by thermal polymerization with phthalic anhydride to give the alkyd resins with molecular weight of several thousands. The reaction of the enzymatically obtained alcoholysis product with toluene diisocyanate produced the alkyd-urethane. 

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