MONOMER RATIO

If TI T2, with both values less than unity, the copolymer starts out richer in monomer 1 than the feed mixture and then crosses the 45° line, and is richer in component 2 beyond this crossover point. At the crossover point the copolymer and feed mixture have the same composition. The monomer ratio at this point is conveniently solved from Eq. (7,15) ... 

Alternation is usually above 90%. Nearly perfect alternation of isomeric units in a ca 1 1 monomer ratio has been confirmed by infrared spectroscopy. Bands at 733 and 721 cm have an intensity proportional to the concentration of (CH2) groups (n = 4 and <6, respectively) present in a copolymer containing 46 mol % tetrafluoroethylene intensity decreases with increasing concentration of fluorinated monomer. 

Polyvinylpyrrohdinone/vinyl acetate copolymer (PVP/VA) was developed as an improved, less hygroscopic version of PVP. The monomer ratios control the stiffness and the resistance to humidity however, too high a vinyl acetate monomer content requires another solvent in addition to water to completely solubilize it. 

Addition of dialkyl fumarates to DAP accelerates polymerization maximum rates are obtained for 1 1 molar feeds (41). Methyl aUyl fumarate [74856-71-6] (MAF), CgH QO, homopolymerizes much faster than methyl aUyl maleate [51304-28-0] (MAM) and gelation occurs at low conversion more cyclization occurs with MAM. The greater reactivity of the fumarate double bond is shown in copolymerization of MAF with styrene in bulk. The maximum rate of copolymerization occurs from monomer ratios, almost 1 1 molar, but no maximum is observed from MAM and styrene. Styrene hinders cyclization of both MAF and MAM. 

Polypyrroles. Highly stable, flexible films of polypyrrole ate obtained by electrolytic oxidation of the appropriate pyrrole monomers (46). The films are not affected by air and can be heated to 250°C with Htde effect. It is beheved that the pyrrole units remain intact and that linking is by the a-carbons. Copolymerization of pyrrole with /V-methy1pyrro1e yields compositions of varying electrical conductivity, depending on the monomer ratio. Conductivities as high as 10 /(n-m) have been reported (47) (see Electrically conductive polymers). 

Type Monomer ratio styrene/butadiene Mooney viscosity, ML-4 SoHds, wt % pH Emulsifier ... 

Various techniques have been studied to increase sohds content. Hydroxy-functional chain-transfer agents, such as 2-mercaptoethanol [60-24-2], C2HgOS, reduce the probabihty of nonfunctional or monofunctional molecules, permitting lower molecular-weight and functional monomer ratios (44). Making low viscosity acryhc resins by free-radical initiated polymerization requires the narrowest possible molecular-weight distribution. This requires carehil control of temperature, initiator concentration, and monomer concentrations during polymerization. 

Nitrile rubbers are produced over a wide range of monomer ratios and molecular weights, so thek physical constants and basic polymer properties also cover a range of values. Some of the more widely used properties are Hsted ki Table 1. 

Ethylene-cyclo-olefin copolymers have been known since 1954 (DuPont USP2 721 189) but these materials only became of importance in the late 1990s with the development of copolymers of ethylene and 2-norbomene by Hoechst and Mitsui using metallocene technology developed by Hoechst. The product is marketed as Topas by Ticona. By adjustment of the monomer ratios polymers with a wide range of Tg values may be obtained including materials that are of potential interest as thermoplastic elastomers. This section considers only thermoplastic materials, cyclo-olefins of interest as elastomers are considered further in Section 11.10. 

Thermoplastics grades have a norbomene content in the range 60-80% with Tg values from 60-180°C, in this range the glass transition being almost linearly related to the norbomene content. The modulus of elasticity increases with norbomene content and for commercial materials is in the range 2600-3200 MPa but density (1.02g/cm), tensile strength 66 MPa and water absorption (<0.01 %) is little affected by the monomer ratio. 

The anomalous effect of the last two rubbers in the table with their low solubility parameters is possibly explained by specific interaction of PVC with carbonyl and carboxyl groups present respectively in the ketone- and fumarate-containing rubbers to give a more than expected measure of compatibility. It is important to note that variation of the monomer ratios in the copolymers and terpolymers by causing changes in the solubility parameter and eompatibility will result in variation in their effect on impact strength. 

An example of the contribution of polar interactions between an acrylic PSA and a substrate is shown in Fig. 6. By copolymerizing iso-octylacrylate and acrylic acid, using a monomer ratio of, respectively, 95/5 and 90/10, two otherwise identical PSAs were made. The PSAs were laminated to both sides of a foam core to make an attachment tape as used in the automotive industry for the application of body side moldings to a car. One side of the foam tape was laminated against an aluminum foil backing. The other side was laminated against an automotive paint-coated panel to make the final test sample. The test sample was allowed to... 

Since 1 is a monomer with low activity, copolymers 2 obtained at any stage of the copolymerization process, irrespective of the monomer ratio in the initial mixture, always contain a smaller amount of monomeric units of 1 than that in the corresponding monomer mixture. 1 being prone to enter the chain-transfer reaction, the increase of its content in the initial monomer mixture reduces substantially the reaction rate and decreases the molecular mass of the copolymers. It was found that copolymers 2 which contain 2—8% of monomeric units of 1 and are suitable for obtaining fibres must have a molecular mass between 45 000 and 50000. Such copolymers can be obtained with a AN 1 ratio in the initial mixture between 95 5 and 85 15. Concentrated solutions of copolymers, especially those with a molecular mass smaller than the above limit, are characterized by a very low stability which is a substantial shortcoming of these copolymers. 

Fig. 1. Dependence of the composition of the copolymer from AN and ISP on the monomers ratio in the initial mix-...

For the case of MMA polymerization with a source of f-butoxy radicals (DBPOX) as initiator and toluene as solvent, most initiation may be by way of solvent-derived radicals"1"" (Scheme 3.9). Thus, a high proportion of chains (>70% for 10% w/v monomers at 60 °C22) will be initiated by benzyl rather than 1-butoxy radicals. Other entities with abstractable hydrogens may also be incorporated as polymer end groups. The significance of these processes increases with the degree of conversion and with the (solvent or impurity) monomer ratio. 

Transfer to initiator can be a major complication in polymerizations initiated by diacyl peroxides. The importance of the process typically increases with monomer conversion and the consequent increase in the [initiator] [monomer] ratio.9 105160 162 In BPO initiated S polymerization, transfer to initiator may be lire major chain termination mechanism. For bulk S polymerization with 0.1 M BPO at 60 °C up to 75% of chains are terminated by transfer to initiator or primary radical termination (<75% conversion).7 A further consequence of the high incidence of chain transfer is that high conversion PS formed with BPO initiator tends to have a much narrower molecular weight distribution than that prepared with other initiators (e.g. AIBN) under similar conditions. 

Studies on the reactions of small model radicals with monomers provide indirect support but do not prove the bootstrap effect.111 Krstina et ahL i showed that the reactivities of MMA and MAN model radicals towards MMA, S and VAc were independent of solvent. However, small but significant solvent effects on reactivity ratios are reported for MMA/VAc111 and MMA S 7 copolymerizations. For the model systems, where there is no polymer coil to solvate, there should be no bootstrap effect and reactivities are determined by the global monomer ratio [Ma0]/[Mb0].1j1... 

Heat transfer problems become more severe as reaction rates are increased and water-to-monomer ratios are reduced. In addition, as reactor sizes are increased for improved process economics, the amount of wall heat transfer surface area per unit volume will drop and result in a lower reactor space-time yield. 

For OMMT content to be 3 wt% and changing the monomer ratio of styrene and butadiene (such as 0 100, 10 90, 25 75, 40 60, 60 40, and 100 0), a series of the polymers-MMT products were prepared, and coded as S-0M3, S-10M3, S-25M3, S-40M3, S-60M3, S-100M3, respectively. 

Molecular structural changes in polyphosphazenes are achieved mainly by macromolecular substitution reactions rather than by variations in monomer types or monomer ratios (1-4). The method makes use of a reactive macromolecular intermediate, poly(dichlorophosphazene) structure (3), that allows the facile replacement of chloro side groups by reactions of this macromolecule with a wide range of chemical reagents. The overall pathway is summarized in Scheme I. 

This applies only to the increment of copolymer formed over a narrow range of conversion and not to the total product, which consists in general of increments formed at progressively changing monomer ratios. 

In summary, the copolymer composition depends on the monomer ratio in the monomer mixture and on r1 and rz reactivity ratios. 

By using a transition metal chloride catalyst and an iodine modified cocatalyst, ring-opening polymerization of C5 and C8 monocyclic olefins is controlled to prepare either cis polymers or trans products that are crystallizable. In copolymerization, the cis/trans units in the copolymers are regulated by adjusting the C5/C8 olefin monomer ratio. As the comonomer is increased, the copolymer becomes less crystalline and then completely amorphous at equal amounts of cis/trans units. Polymerization results are reported from WC16 and MoCl5 catalysts. 

Two macroinitiators carrying PEOs of different molar masses (Mw = 550 or 1900 g molx) were used. By varying the initiator and the initiator-to-monomer ratio, a series of block copolymers was obtained (Table 2). The copolymers (NE) with the longer (1900 g mol-1) PEO block are designated with capital letters A-C, and those with the shorter block (550 g mol-1) with numbers 1-3. Block copolymers having the same PEO block form what is called a copolymer set. 

Fig. 3. Electron micrographs of polymer particles formed by emulsion polymerization of 1,4-DVB and S [79], SDS concentration = 0.02 M, Initiator concentration = 0.01 M, temperature = 50 °C, water/monomer ratio = 6.25. [Reproduced from Ref. 79 with permission, Huthig Wepf Publ., Zug, Switzerland].

Fig. 8. Variationof the weight-average molar mass Mw ( ) and z-average hydrodynamic diameter in toluene dz (o) with the emulsifier concentration in the emulsion polymerization of 1,4-DVB [83]. Polymerization temperature = 70 °C, initiator = AIBN, water/monomer ratio = 12.5.

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