Solid polymerisation

The yellow solid polymerises irreversibly at room temperature giving an insoluble brick-red material. The dimer oxidises iodides to iodine and Cu+ to Cu + ions. 

If aldehyde is cooled and treated with sulphuric acid, or if at the ordinary temperature gaseous hydrochloric add, sulphur dioxide, or other compounds are passed into it, a solid polymerisation product,... 

Liquid - solid Polymerisation by local UV exposure of a photosensitive resin Photosensitive resins Acrylates, epoxydes shrinkage and deformations model needs supports... 

Formaldehyde is used commercially either as its aqueous solution or in a solid polymerised form. 

Silicon difluoride is obtained as a very reactive gas when silicon tetrafluoride and silicon are heated together. It polymerises rapidly to give (SiF2) , a solid. 

It is a white, deliquescent solid, very powdery, which exhibits polymorphism on heating, several different crystalline forms appear over definite ranges of temperature -ultimately, the P4O10 unit in the crystal disappears and a polymerised glass is obtained, which melts to a clear liquid. 

Polymerisation. To 0 5 ml. of styrene add i drop of cone. HjSOj. Note the formation of a solid glassy mass of polystyrene. 

Solubility in concentrated sulphuric acid. Place 3 0 ml. of pure concentrated sulphuric acid in a dry test-tube and add 0 -10 g. of a solid or 0 -20 ml. of a liquid. If the compound does not dissolve immediately, agitate for some time but do not heat. Observe any change in colour, charring, evolution of gaseous products, polymerisation accompanied by precipitation etc. 

In all of the examples given so far in this chapter the product of polymerisation has been a long chain molecule, a linear polymer. With such materials it should be possible for the molecules to slide past each other under shear forces above a certain temperature such that the molecules have enough energy to overcome the intermolecular attractions. In other words above a certain temperature the material is capable of flow, i.e. it is essentially plastic, whereas below this temperature it is to all intents and purposes a solid. Such materials are referred to as thermoplastics and today these may be considered to be the most important class of plastics material commercially available. 

A number of olefins may be polymerised using certain metal oxides supported on the surface of an inert solid particle. The mechanism of these polymerisation reactions is little understood but is believed to be ionic in nature. 

Bulk polymerisation is heterogeneous since the polymer is insoluble in the monomer. The reaction is autocatalysed by the presence of solid polymer whilst the concentration of initiator has little effect on the molecular weight. This is believed to be due to the overriding effect of monomer transfer reactions on the chain length. As in all vinyl chloride polymerisation oxygen has a profound inhibiting effect. 

Polymerisation may be carried out by techniques akin to those used in the manufacture of PTFE. The preparation of polymers in yields of up to 88% are described in one patent. Water was used as a diluent in concentrations of from one to five times the weight of the monomer, a gas with boiling point of -27.9°C. Solid polymers were formed with reaction temperatures of CL40°C at higher reaction temperatures liquid polymers are formed. 

These materials have been prepared by polymerisation of p-halothiophenoxide metal compounds both in the solid state and in solution. They have also been prepared by condensation of p-dichlorobenzene with elemental sulphur in the presence of sodium carbonate while the commercial polymers are said to be produced by the reaction of p-dichlorobenzene with sodium sulphide in a polar solvent. 

PET suitable for bottle manufacture is produced by a modified process. Here the high-viscosity polymer melt is subjected to a rapid quenching in water to produce clear amoiphous pellets. These are further polymerised in the solid phase at temperatures just below the T . This is useful to reduce aldehyde content, since aldehyde-forming degradation reactions occur less in the lower temperature solid phase polymerisations. Aldehydes can impart a taste to beverages and it is important to keep the aldehyde content to below 2.5 p.p.m. 

The situation is confused, however, by the case of certain chemicals. Styrene, for example, was known from the mid-nineteenth century as a clear organic liquid of characteristic pungent odour. It was also known to convert itself under certain circumstances into a clear resinous solid that was almost odour-free, this resin then being called metastyrene. The formation of metastyrene from styrene was described as a polymerisation and metastyrene was held to be a polymer of styrene. However, these terms applied only in the sense that there was no change in empirical formula despite the very profound alteration in chemical and physical properties. There was no understanding of the cause of this change and certainly the chemists of the time had no idea of what had happened to the styrene that was remotely akin to the modem view of polymerisation. 

As emulsion polymerisation proceeds, like the suspension technique but unlike either the bulk or the solution techniques, there is almost no increase in viscosity. The resulting dispersed polymer is not a true emulsion any more, but instead has become a latex. The particles of the latex do not interact with the water hence viscosity is not found to change significantly up to about 60% solids content. 

This involves subjecting a polymer, such as PMMA, in solid, gel, partially molten or molten form to microwave heating for a time and at a temperature sufficient to decompose the polymer to produce a monomer or monomers in gaseous, liquid or solid form, without substantial decomposition of the monomer or monomers, and recovering at least one of the monomer or monomers. The monomer or monomers may then be reused for polymerisation. 

A method for the depolymerisation of PETP fibres using quarternary ammonium salt phase transfer catalysts in saponification processes at atmospheric pressure and temperatures as low as room temperature is reported. Terephthalic acid was produced in yields as high as 93%. Also reported are similar processes for the depolymerisation of nylon 66 and nylon 46 fibres. Nylon 46 oligomers produced were repolymerised using solid-state polymerisation to produce high molecular weight nylon 46. Nylon 66 was depolymerised to produce oligomers and adipic acid in reasonable yields. 11 refs. USA... 

Section 3 deals with reactions in which at least one of the reactants is an inorganic compound. Many of the processes considered also involve organic compounds, but autocatalytic oxidations and flames, polymerisation and reactions of metals themselves and of certain unstable ionic species, e.g. the solvated electron, are discussed in later sections. Where appropriate, the effects of low and high energy radiation are considered, as are gas and condensed phase systems but not fully heterogeneous processes or solid reactions. Rate parameters of individual elementary steps, as well as of overall reactions, are given if available. 

This salt is used as an inhibitor for the polymerisation of butadiene. It seems to play its role very well when its concentration is lower than 0.5%. If the concentration is greater than 5%, a black precipitate forms which contains 80% of organic polymer containing nitrate and nitrite groups in the proportions of 2 1. This solid combusts spontaneously at 150 C even when there is no air. 

Accidents are often caused by the violent polymerisation of aziridine. To avoid it, this amine needs to be handled or stored in a diluted solution when it is cold, and alkaline hydroxide in the solid state is present. 

It is marketed as a 35-40 per cent, solution in water (formalin). The rpactions of formaldehyde are partly typical of aldehydes and partly peculiar to itself. By evaporating an aqueous solution paraformaldehyde or paraform (CH O), an amorphous white solid is produced it is insoluble in most solvents. When formaldehyde is distilled from a 60 ptr cent, solution containing 2 per cent, of sulphuric acid, it polymerises to a crystalline trimeride, trioxane, which can be extracted with methylene chloride this is crystalline (m.p. 62°, b.p. 115°), readily soluble in water, alcohol and ether, and devoid of aldehydic properties ... 

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