Polymerisation viscosity increase

In solution polymerisation, the reaction is carried out in presence of a solvent. The monomer is dissolved in a suitable inert solvent along with the chain transfer agent. A large number of initiators can be used in this process. The free radical initiator is also dissolved in the solvent. The ionic and coordination catalysts can either be dissolved or suspended in the medium. The solvent facilitates the contact of monomer and initiator and helps the process of dissipation of exothermic heat of reaction. It also helps to control viscosity increase. 

When the reaction becomes diffusion controlled as a result of the increased viscosity of the oil, alkoxy radicals can initiate polymerisation of polycondensation products. This leads to sludge and deposit formation as well as to additional oil-soluble high molecular weight products which contribute to the viscosity increase. This process can be described as co-polymerisation of two different polycondensation species in which the alkyl groups R, R and R could represent 0x0- or hydroxy-functionalised long hydrocarbon chains Reaction (4.23) ... 

VISCOSITY OF ONE-COMPONENT SOLS a. Viscosity increase on polymerisation... 

Starting from this point of view, the viscosity increase on polymerisation can easily be understood. The transition of the smaller molecules into large ones has two consequences n. an increase of the size and... 

As the polymer molecules form and dissociate from the catalyst, they remain ia solution. The viscosity of the solution increases with increasing polymer concentration. The practical upper limit of solution viscosity is dictated by considerations of heat transfer, mass transfer, and fluid flow. At a mbber soflds concentration of 8—10%, a further increase in the solution viscosity becomes impractical, and the polymerisation is stopped hy killing the catalyst. This is usually done by vigorously stirring the solution with water. If this is not done quickly, the unkilled catalyst continues to react, leading to uncontrolled side reactions, resulting in an increase in Mooney viscosity called Mooney Jumping. 

The explanation for autoacceleration is as follows. As polymerisation proceeds there is an increase in the viscosity of the reaction mixture which reduces the mobility of the reacting species. Growing polymer molecules are more affected by this than either the molecules of monomer or the fragments arising from decomposition of the initiator. Hence termination reactions slow down and eventually stop, while initiation and propagation reactions still continue. Such a decrease in the rate of the termination steps thus leads to the observed increase in the overall rate 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. 

The practical effect shown by this equation is that polymers become more difficult to process as their molar mass increases. For example, doubling the degree of polymerisation leads to an approximately ten-fold increase in melt viscosity. Fortunately, melt viscosity decreases with increasing temperature, so that in many cases the effect of high viscosity for higher molar masses can be overcome. However, there is an upper limit at which polymers can be processed without beginning to degrade so it follows that, at some point, a polymer cannot be processed from the melt at all. 

The rheological behaviour of polymeric solutions is strongly influenced by the conformation of the polymer. In principle one has to deal with three different conformations, namely (1) random coil polymers (2) semi-flexible rod-like macromolecules and (2) rigid rods. It is easily understood that the hydrody-namically effective volume increases in the sequence mentioned, i.e. molecules with an equal degree of polymerisation exhibit drastically larger viscosities in a rod-like conformation than as statistical coil molecules. An experimental parameter, easily determined, for the conformation of a polymer is the exponent a of the Mark-Houwink relationship [25,26]. In the case of coiled polymers a is between 0.5 and 0.9,semi-flexible rods exhibit values between 1 and 1.3, whereas for an ideal rod the intrinsic viscosity is found to be proportional to M2. 

Biesenberg, J. S. etal., J. Polym. Eng. Sci., 1976,16, 101-116 Polymerisation of methyl methacrylate initiated by oxygen or peroxides proceeds with a steady increase in velocity during a variable induction period, at the end of which a violent 90°C exotherm occurs. This was attributed to an increase in chain branching, and not to a decrease in heat transfer arising from the increasing viscosity [ 1 ]. The parameters were determined in a batch reactor for thermal runaway polymerisation of methyl methacrylate, initiated by azoisobutyronitrile, dibenzoyl peroxide or di-ferf-butyl peroxide [2],... 

Performing what is known as post-condensation. Most step polymerisations are exothermic and, consequently, the equilibrium constant K decreases with increasing temperature. Hence, one way to increase the molecular mass would be to decrease the polymerisation temperature, but kinetics prohibits using a too low temperature as it will lead to an excessively long residence time in the reactor and/or too high viscosities. Thus, in order to reach very high molecular... 

Since most of our observations on the reacting systems were made by means of conductivity measurements it is necessary to remember that in these systems the only factor which increases conductivity is an increase in the concentration of ions, but that a decrease of conductivity could be due to any or all of the following effects increase of size of cation by polymerisation, increase of viscosity of solvent due to polymer, occlusion of ions in precipitated polymer, trapping of polymer between the electrodes. A similar list was given by Matyska in one of the earliest applications of conductivity measurements to a cationic polymerisation, that of isoprene by aluminium bromide in toluene solvent [19]. 

Miyata and Nakashio [77] studied the effect of frequency and intensity on the thermally initiated (AIBN) bulk polymerisation of styrene and found that whilst the mechanism of polymerisation was not affected by the presence of ultrasound, the overall rate constant, k, decreased linearly with increase in the intensity whilst the average R.M.M. increased slightly. The decrease in the overall value of k they interpreted as being caused by either an increase in the termination reaction, specifically the termination rate constant, k, or a decrease in the initiator efficiency. The increase in kj(= kj /ri is the more reasonable in that ultrasound is known to reduce the viscosity of polymer solutions. This reduction in viscosity and consequent increase in Iq could account for our observed reductions [78] in initial rate of polymerisation of N-vinyl-pyrrolidone in water. However this explanation does not account for the large rate increase observed for the pure monomer system. 

Polystyrene latexes were similarly prepared by Ruckenstein and Kim [157]. Highly concentrated emulsions of styrene in aqueous solutions of sodium dodecylsulphate, on polymerisation, yielded uncrosslinked polystyrene particles, polyhedral in shape and of relative size monodispersity. Interestingly, Ruckenstein and coworker found that both conversions and molecular weights were higher compared to bulk polymerisation. This was attributed to a gel effect, where the mobility of the growing polymer chains inside the droplets is reduced, due to increased viscosity. Therefore, the termination rate decreases. 

The state of aggregation of the polymerising system represents another important factor which may affect the kinetics of polymerisation. It is well known (96,97) that many radical polymerisations are enhanced by increase in the viscosity of the po-lymerisingsystem, and this phenomenon was explained by a decrease in the rate of termination step which may become diffusion-controlled. In fact, the effect of viscosity should be observed at any stage of radical polymerisation, and this problem has been discussed recently by Benson and North (98, 99). Of course, this type of acceleration cannot be observed when the growth involves living polymers and therefore such an explanation does not apply to polymerisation of NCA, particularly since no termination resulting from active end-active end interaction takes place in these processes. 

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