Polymerisation solution phase

In some processes, a diluent, like benzene or chlorobenzene are used as the solvent. At high pressure and temperature, both the polyethylene and the monomers dissolve in these solvents so that the reaction occur in a solution phase. In a typical process, 10-30 per cent of the monomer is converted to polymer per cycle. Rest of monomer is recycled. Extensive chain transfer reactions take place during polymerisation to yield a branched polyethylene. Apart from long branches it is also having a large number of short branches of unto 5 carbon atoms formed by intramolecular chain transfer reactions. A typical molecule of Low density polyethylene is having a short branch for about every 50 carbon atoms and one or two long branches per molecule. 

Self-supported MIP membranes can be seen as an alternative format to the traditional MIP particles for applications in separation and sensor technology, avoiding the limitations of mass transfer across conventional MIP materials. Two main approaches have been used for the preparation of membranes composed of an MIP in situ polymerisation and polymer solution phase inversion. 

A summary of the properties of polymers prepared chemically and electrochemically is shown in Table 3. The sizable differences in the ultraviolet absorption maxima is only apparent as the electrochemically polymerised samples were recorded as thin films on ITO glass whilst the chemically polymerised samples were recorded as solutions in NMP. Such hypsochromic changes in nre expected in going from the solid to solution phases and were borne out in model studies Although the conductivities of the polymers were of the order of 10 2 S cm-, these polymers were found to be soluble in a number of solvents (Table 4) in contrast to the total lack of solubility of polythiophene. 

Next to homogeneous reaction conditions, multi-phase or heterogeneous polymerisation conditions frequently occur. Suspension and emulsion polymerisation are examples, but also condensation polymerisation with phase separation of water during cure. The low-temperature production of inorganic polymer glasses (IPGs) is a special case of suspension polymerisation involving clay particles in a reactive silicate solution. 

Fig. 2.1. Schematic illustration of polyethylene molecular structure of various density ranges (Elias 1992). Top LDPE, radical polymerisation yields a number of (long) side ehains. Bottom HDPE, catalytic polymerisation gives rise to linear ehains with a small number of short branches. Both drawings in the middle illustrate LLDPEs produced by catalytic polymerisation with a-olefines. Small amounts of bntene-1, hexene-1 or octene-1 co-monomers lead to etlyl, butyl or hexyl side chains. Polymerisation in the gaseous phase produces chains arranged in a block-shaped fashion and distributed at various frequencies along the chaia Solution phase polymerisation provides a statistical random distribution along the whole chain...

Fig. 2.2. Simplified flow chart of the Phillips process (solution phase polymerisation) (Elias 1992). The solvent (for example isobutane), ethylene, co-monomers and the catalyst are fed into the reactor. The polymer solution is de sed (flashed) from the reactor through a gas separator after a certain reaction time. In a cleaning nnit (centrifuge, washing device, drier) the polymer is separated out and ethylene and solvent residues are processed. The polymer emerges in the drier in the form of snow white flakes. Flakes, carbon black, stabiliser and further additives, for example Ca-stearate, are mixed in a mixer and this mix is fed into an ex-tmder at an adequate mix raho with the polymer flakes. Here the mix is melted, homogenised and finally granulated. The black pellets are then transported to the storage facihties...

The technologies suitable for LLDPE manufacture include gas-phase fluidised-bed polymerisation, polymerisation in solution, polymerisation in a polymer melt under high ethylene pressure, and slurry polymerisation. Most catalysts are fine-tuned for each particular process. 

EPM and EPDM mbbers are produced in continuous processes. Most widely used are solution processes, in which the polymer produced is in the dissolved state in a hydrocarbon solvent (eg, hexane). These processes can be grouped into those in which the reactor is completely filled with the Hquid phase, and those in which the reactor contents consist pardy of gas and pardy of a Hquid phase. In the first case the heat of reaction, ca 2500 kJ (598 kcal)/kg EPDM, is removed by means of cooling systems, either external cooling of the reactor wall or deep-cooling of the reactor feed. In the second case the evaporation heat from unreacted monomers also removes most of the heat of reaction. In other processes using Hquid propylene as a dispersing agent, the polymer is present in the reactor as a suspension. In this case the heat of polymerisation is removed mainly by monomer evaporation. 

Furthermore, should free radicals be present, the vinyl groups would much more rapidly polymerise depleting the emulsion droplets of monomer, providing the control required for a particular particle size. The composition of the solution thus determines not only the phase behaviour, but the rate of polymerisation and the particle size. If, the organism has in its genetic code, the abihty to synthesise the monomer, it presumably has... 

As Skinner has pointed out [7], there is no evidence for the existence of BFyH20 in the gas phase at ordinary temperatures, and the solid monohydrate of BF3 owes its stability to the lattice energy thus D(BF3 - OH2) must be very small. The calculation of AH2 shows that even if BFyH20 could exist in solution as isolated molecules at low temperatures, reaction (3) would not take place. We conclude therefore that proton transfer to the complex anion cannot occur in this system and that there is probably no true termination except by impurities. The only termination reactions which have been definitely established in cationic polymerisations have been described before [2, 8], and cannot at present be discussed profitably in terms of their energetics. It should be noted, however, that in systems such as styrene-S C/4 the smaller proton affinity of the dead (unsaturated or cyclised) polymer, coupled, with the greater size of the anion and smaller size of the cation may make AHX much less positive so that reaction (2) may then be possible because AG° 0. This would mean that the equilibrium between initiation and termination is in an intermediate position. 

In order to study the variation of the concentration of ions during and after polymerisation, we scanned the solutions at 424 mp. against time. We found that, in addition to the SD ions, several other species giving peaks in the visible were formed at the end of the polymerisation. Therefore the kinetic study on the formation of the SD ions had to be supplemented by repeated scannings of the full visible and UV spectra. Some of the experiments carried out in the spectroscopic device were repeated in the conductivity cell. In view of the rather complicated behaviour of the system after the end of the polymerisation, we shall first give a chronological account of the phenomena, and then discuss their quantitative aspects. Figure 1 illustrates the different phases of the reaction from a spectroscopic point of view. 

PolyHIPE has found a successful application in the field of solid phase peptide synthesis (SPPS), where the highly porous microstructure acts as a support material for a polyamide gel [134]. The polystyrene matrix is functionalised to give vinyl groups on its internal surfaces, and is then impregnated with a DMF solution of N, JV -dimethylacrylamide, acryloylsarcosine methyl ester, crosslinker and initiator. Polymerisation grafts the soft gel onto the rigid support, giving a novel composite material (Fig. 16). 

Rubber-toughened polystyrene composites were obtained similarly by polymerising the dispersed phase of a styrene/SBS solution o/w HIPE [171], or a styrene/MMA/(SBS or butyl methacrylate) o/w HIPE [172], The latter materials were found to be tougher, however, all polymer composites had mechanical properties comparable to bulk materials. Other rubber composite materials have been prepared from PVC and poly(butyl methacrylate) (PBMA) [173], via three routes a) blending partially polymerised o/w HIPEs of vi-nylidene chloride (VDC) and BMA, followed by complete polymerisation b) employing a solution of PBMA in VDC as the dispersed phase, with subsequent polymerisation and c) blending partially polymerised VDC HIPE with BMA monomer, then polymerisation. All materials obtained possessed mixtures of both homopolymers plus some copolymer, and had better mechanical properties than the linear copolymers. The third method was found to produce the best material. 

Water-in-oil concentrated emulsions have also been utilised in the preparation of polymer latexes, from hydrophilic, water-soluble monomers. Kim and Ruckenstein [178] reported the preparation of polyacrylamide particles from a HIPE of aqueous acrylamide solution in a non-polar organic solvent, such as decane, stabilised by sorbitan monooleate (Span 80). The stability of the emulsion decreased when the weight fraction of acrylamide in the aqueous phase exceeded 0.2, since acrylamide is more hydrophobic than water. Another point of note is that the molecular weights obtained were lower compared to solution polymerisation of acrylamide. This was probably due to a degree of termination by chain transfer from the tertiary hydroxyl groups on the surfactant head group. 

Crosslinked polyacrylamide latexes encapsulating microparticles of silica and alumina have also been prepared by this method [179], Three steps are involved a) formation of a stable colloidal dispersion of the inorganic particles in an aqueous solution containing acrylamide, crosslinker, dispersant, and initiator b) HIPE preparation with this aqueous solution as the dispersed phase and c) polymerisation. The latex particles are polyhedral in shape, shown clearly by excellent scanning electron micrographs, and have sizes of between 1 and 5 pm. 

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