Polymerisation stability

A monomer preemulsion, used for miniemulsion polymerisation, was prepared by stirring a mixture of epoxy resin, acrylic monomers, surfactants, costabiliser and water. Miniemulsion polymerisation produced the composite latex. Methacrylic acid and/or dimethylaminoethyl methacrylate were added to introduce the functional groups into the composite latices. The functional groups were introduced either by batch polymerisation or two-stage polymerisation, the latex produced by the two-stage polymerisation method had good polymerisation stability, storage stability and solvent resistance. 11 refs. 

Staudinger also found that diacetates of polyoxymethylenes with a degree of polymerisation of about 50 were less stable. Truly high molecular weight polyoxymethylenes (degree of polymerisation -1000) were not esterified by Staudinger this was effected by the Du Pont research team and was found to improve the thermal stability of the polymer substantially. 

The stability of the copolymers may be enhanced by alkaline hydrolysis following polymerisation to remove oxymethyl end-groups and replace them with the more stable oxyethyl groups. 

A bacterial isolate APN has been shown to convert a-aminopropionitril enantioselectively to L-alanine (94% yield, 75% e e). However, the major disadvantage of this approach, is the low stability of most aminonitriles in water (for example a-aminophenylacetonitrile in water of pH 7, degrades completely within 48 hours). The aminonitriles are always in equilibrium with the aldehyde or ketone and ammonia/HCN. Polymerisation of hydrogen cyanide gives an equilibrium shift resulting in the loss of the aminonitrile. Therefore, a low yield in amino adds is to be expected, which makes this method less attractive for the industrial synthesis of optically active amino adds. 

However, other molecules exist which form free radicals of such high stability that they effectively stop the chain process. These molecules are called retarders or inhibitors the difference is one of degree, retarders merely slowing down the polymerisation reaction while inhibitors stop it completely. In practice vinyl monomers such as styrene and methyl methacrylate are stored with a trace of inhibitor in them to prevent any uncontrolled polymerisation before use. Prior to polymerisation these liquids must be freed from this inhibitor, often by aqueous extraction and/or distillation. 

Amine-containing accelerators and stabilizers used in the polymerisation of rubber latex... 

Aziridine is the only one that has a serious instability risk according to CHETAH. It is due to the presence of a strained ring, which gives an endothermic character to the compound. As its stability should be more or less the same as ethylene oxide, so should be its propensity for polymerisation. 

Here is a list of all dangerous reactions that are related to nitrile functional group behaviour. By active polymerisation is meant the polymerisation that affects the carbon-nitrogen triple bond. Polymerisations that are related to an ethylene double bond will be dealt with on p.336. So far as stability is concerned, it is difficult to say whether certain spontaneous reactions of certain nitriles are... 

At 130°C or at ambient temperature and in the presence of bases, malonitrile gives rise to a very violent polymerisation. The stability of this dinitrile in the molten state (mp 32°C) decreases with the temperature rise and its fall in purity. It was assumed that decomposition never occurs below 100 C. However, when this compound was heated to 70-80°C for two months, this caused a very violent detonation. 

There are reports of polymerisation of pyrrole [161, 162] and aniline [163] onto polyacetylene, to give oxygen and water stability [161], although there is some evidence for the polyacetylene acting electrocatalytically, oxidizing the pyrrole with no concomitant polymerisation. 

SELF-HEATING AND IGNITION INCIDENTS THERMAL STABILITY OF REACTION MIXTURES VIOLENT POLYMERISATION... 

It may polymerise violently on heating at 130°C, or in contact with strong bases at lower temperatures [1], The stability of the molten nitrile decreases with increasing temperature and decreasing purity, but no violent decomposition below 100°C has been recorded [2], However, a partially filled drum of malononitrile stored in an oven at 70-80°C for 2 months exploded violently [3],... 

Dartnell, R. C. et al., Loss Prev., 1971, 5, 53-56 MCA Case History No. 1649 A batch of 8 t of material accumulated in storage at 154°C during 72 h decomposed explosively. Stability tests showed that thermal instability developed when 3-methyl-4-nitrophenol is stored molten at temperatures above 140°C. Decomposition set in after 14 h at 185° or 45 h at 165°, with peak temperatures of 593 and 521°C, respectively. In a closed vessel, a peak pressure of 750 bar was attained, with a maximum rate of increase of 40 kbar/s. Thermal degradation involves an initially slow exothermic free radical polymerisation process, followed by a rapid and violently exothermic decomposition at take-off. 

Unlike radical chain polymerisation, initiation in cationic polymerisation uses a true catalyst that is recovered at the end of the polymerisation and is not incorporated at one end of the growing chain. Catalysts for cationic chain polymerisation are molecules able to withdraw electrons, mainly Bronsted (H2SC>4, H3PO4) and Lewis acids (BF3, A1C13, SnCh). The choice of solvent for cationic polymerisation is also important because it plays a major role in the association between cation and counter ion. A too tight association will prevent monomer insertion during the propagation step. However, the use of "stabilized"... 

A more recent, extended study of purine synthesis via polymerisation of ammonium cyanide, described at the beginning of this section, showed that the yield of adenine from the non-hydrolyzed solution was only slightly temperature dependent. Shorter hydrolysis times for the insoluble polymerisation products led to higher adenine yields. When the solution is hydrolyzed at pH 8, the adenine yield is comparable to the value of 0.1% found for acidic hydrolysis (a model for the primeval ocean ). Increasing the hydrolysis time has no effect on the adenine yield because of its greater stability at pH 8. Hydrolysis of the black NH4CN polymer under acidic or neutral conditions results in an adenine yield of about 0.05% (Borquez et al., 2005). 

Novel thermally responsive polymeric nanoparticles that show high colloidal stability were prepared by Laukkanen et al. via emulsion polymerisation of VCL in the presence of the amphiphilic macromonomer cw-methoxy polyethylene oxide undecyl a-methacrylate (MAC11EO42) (Fig. 15) [177,178,182]. The macromonomer itself proved to be highly sur-... 

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