Degree of polymerisation

Investigation has shown that chain transfer to polymer occurs predominantly on the acetate methyl group in preference to the chain backbone one estimate of the magnitude of the predominance is 40-fold (92,93). The number of branches per molecule of poly(vinyl acetate) polymerised at 60°C is ca 3, at 80% conversion. It rises rapidly thereafter and is ca 15 at 95% conversion and 1-2 x lO" number-average degrees of polymerisation. 

With decreasing amounts of metal oxide, the degree of polymerisation increases. Chains of linked tetrahedra form, like the long chain polymers with a -C-C- backbone, except that here the backbone is an -Si-O-Si-O-Si- chain (Fig. 16.4c). Two oxygens of each tetrahedron are shared (there are two bridging oxygens). The others form ionic bonds between chains, joined by the MO. These are weaker than the -Si-O-Si- bonds which form the backbone, so these silicates are fibrous asbestos, for instance, has this structure. 

The number average degree of polymerisation x is defined as the average number of monomer units per polymer chain. Therefore if termination is by disproportionation r = jc, but if by combination r = x. 

In many technical polymerisations transfer reactions to modifier, solvent, monomer and even initiator may occur. In these cases whereas the overall propagation rate is unaffected the additional ways of terminating a growing chain will cause a reduction in the degree of polymerisation. 

Figure 2.19. Effect of chain transfer solvents on the degree of polymerisation of polystyrene. (After...

Transfer reactions will reduce the degree of polymerisation without affecting the rate of conversion. 

It follows immediately that the number average degree of polymerisation is given by ... 

In the case of linear polymers it is often difficult to obtain high molecular weight polymers. The degree of polymerisation i will be given by... 

Thus when 95% of the groups have reacted (/ = 0.95) the degree of polymerisation will be only 20. 

Assuming that in polyethylene the polarisation is solely electronic, that the degree of polymerisation is r and that the repeating unit is as shown in Figure 6.7. 

A number of grades of poly(vinyl formal) are commercially available (Formvar, Mowital) which vary in degree of polymerisation, hydroxyl content and residual acetate content. 

As with poly(vinyl alcohol), poly(vinyl cinnamate) is prepared by chemical modification of another polymer rather than from monomer . One process is to treat poly(vinyl alcohol) with cinnamoyl chloride and pyridine but this is rather slow. Use of the Schotten Baumann reaction will, however, allow esterification to proceed at a reasonable rate. In one example poly(vinyl alcohol) of degree of polymerisation 1400 and degree of saponification of 95% was dissolved in water. To this was added a concentrated potassium hydroxide solution and then cinnamoyl chloride in methyl ethyl ketone. The product was, in effect a vinyl alcohol-vinyl cinnamate copolymer Figure 14.8)... 

The products betu a strong formal resemblance to styrene and may be polymerised. For commercial purposes the monomers are not separated but are polymerised in situ in the crude naphtha, sulphuric acid acting as an ionic catalyst to give polymers with a degree of polymerisation of 20-25. 

The cyclic trimer (trioxane) and tetramer are obtained by a trace of sulphuric acid acting on hot formaldehyde vapour (i) Figure 19.1). Linear polymers with degrees of polymerisation of about 50 and a terminal hydroxyl group are obtained by evaporation of aqueous solutions of formaldehyde (ii). In the presence of strong acid the average chain length may be doubled. Evaporation of methanol solution leads to products of type (iii). 

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. 

Controlled polymerisation of ethylene oxide under alkaline conditions will produce a range of polymers marketed under the trade name Carbowax. These have molecular weights in the range 1500-20000 and are greases or waxes according to their degree of polymerisation. Lower molecular weight polymers... 

By reduction in the degree of polymerisation. To produce processable rubbers the original polymers are masticated with substances such as benzothiazole disulphide and tetramethylthiuram disulphide. The more severe degradation techniques to produce liquid polysulphides are mentioned below. 

This involves first the preparation of lower molecular weight polymers with a degree of polymerisation of about three. These are then reacted with bis-phenol A in the presence of a suitable polymerisation catalyst such that the reaction takes place without the evolution of by-products. ... 

Thus hexamethylsilane may be referred to as M-M or M2. A linear silicone polymer with a degree of polymerisation of n would be referred to as MD 2 M. The compound... 

Fig. 4. The effect of chain pull-out of PVP on for three PS-PVP diblocks whose PVP block varied from degree of polymerisation 49 to 220 [4].

These effects have been found by Creton et al. [79] who laminated sheets of incompatible polymers, PMMA and PPO, and studied the adhesion using a double cantilever beam test to evaluate fracture toughness Fc. For the original laminate Fc was only 2 J/m, but when interface reinforced with increasing amounts of a symmetrical P.M.M.A.-P.S. diblock copolymer of high degree of polymerisation (A > A e), the fracture toughness increased to around 170 J/m, and then fell to a steady value of 70 J/m (Fig. 9). 

Synthetic large molecules are made by joining together thousands of small molecular units known as monomers. The process of joining the molecules is called polymerisation and the number of these units in the long molecule is known as the degree of polymerisation. The names of many polymers consist of the name of the monomer with the suffix poly-. For example, the polymers polypropylene and polystryene are produced from propylene and styrene respectively. Names, and symbols for common polymers are given in Appendix F. 

The size of a polymer molecule may be defined either by its mass (see Chapter 6) or by the number of repeat units in the molecule. This latter indicator of size is called the degree of polymerisation, DP. The relative molar mass of the polymer is thus the product of the relative molar mass of the repeat unit and the DP. 

Step polymerisation Monomer concentration drops rapidly to zero early in the reaction. Polymer molar mass rises steadily during reaction. Long reaction times increase molar mass and are essential to obtain very high molar masses. At all stages of the reaction every possible molecular species from dimers to polymers of large degrees of polymerisation are present in a calculable distribution. 

---