Reactivity ratios butadiene-styrene monomers

The counterion also has a dramatic effect on copolymerization behavior for styrene and dienes [61]. It is particularly noteworthy that the monomer reactivity ratios for styrene (r = 0.42) and butadiene (rg = 0.30) are almost equal for copolymerization in toluene at 20 °C using a hydrocarbon-soluble organosodium initiator 2-ethylhexylsodium [210,211]. Thus, an alternating-type copolymer structure (r rg = 0.126) would be formed for this system however, butadiene is incorporated predominantly as vinyl units (60% 1,2). In contrast, initial preferential styrene incorporation (r = 3.3 rg = 0.12) is observed for an analogous organopotassium initiator, the DPE adduct of 2-ethylhexylpotassium [61]. 

Tapered Block Copolymers. The alkyllithium-initiated copolymerizations of styrene with dienes, especially isoprene and butadiene, have been extensively investigated and illustrate the important aspects of anionic copolymerization. As shown in Table 15, monomer reactivity ratios for dienes copolymerizing with styrene in hydrocarbon solution range from approximately 8 to 17, while the corresponding monomer reactivity ratios for styrene vary from 0.04 to 0.25. Thus, butadiene and isoprene are preferentially incorporated into the copolymer initially. This type of copolymer composition is described as either a tapered block copolymer or a graded block copolymer. The monomer sequence distribution can be described by the structures below ... 

Compositionally uniform copolymers of tributyltin methacrylate (TBTM) and methyl methacrylate (MMA) are produced in a free running batch process by virtue of the monomer reactivity ratios for this combination of monomers (r (TBTM) = 0.96, r (MMA) = 1.0 at 80°C). Compositional ly homogeneous terpolymers were synthesised by keeping constant the instantaneous ratio of the three monomers in the reactor through the addition of the more reactive monomer (or monomers) at an appropriate rate. This procedure has been used by Guyot et al 6 in the preparation of butadiene-acrylonitrile emulsion copolymers and by Johnson et al (7) in the solution copolymerisation of styrene with methyl acrylate. 

There are few studies of the effect of temperature on monomer reactivity ratios [Morton, 1983]. For styrene-1,3-butadiene copolymerization by r-butyllithium in rc-hexane, there is negligible change in r values with temperature with r — 0.03, r2 = 13.3 at 0°C and n = 0.04, r% = 11.8 at 50°C. There is, however, a signihcant effect of temperature for copolymerization in tetrahydrofuran with r — 11.0, r2 = 0.04 at —78°C and r — 4.00, r2 = 0.30 at 25° C. The difference between copolymerization in polar and nonpolar solvents is attributed to preferential complexing of propagating centers and counterion by 1,3-butadiene as described previously. The change in r values in polar solvent is attributed to the same phenomenon. The extent of solvation decreases with increasing temperature, and this results in... 

Using the Q and e values in Table 6-7, calculate the monomer reactivity ratios for the comonomer pairs styrene-1,3-butadiene and styrene-methyl methacrylate. Compare the results with the r and rx values in Table 6.2. 

An alternative rationale for the unusual RLi (hydrocarbon) copolymerization of butadiene and styrene has been presented by O Driscoll and Kuntz (71). Rather than invoking selective solvation, these workers stated that classical copolymerization kinetics is sufficient to explain this copolymerization. They adapted the copolymer-composition equation, originally derived from steady-state assumptions for free-radical copolymerizations, to the anionic copolymerization of butadiene and styrene. Equation (20) describes the relationship between the instantaneous copolymer composition c/[M,]/rf[M2] with the concentrations of the two monomers in the feed, M, and M2, and the reactivity ratios, rt, r2, of the monomers. The rx and r2 values are measures of the preference of the growing chain ends for like or unlike monomers. 

While the majority of SBC products possess discrete styrene and diene blocks, some discussion of the copolymerization of styrene and diene monomers is warranted. While the rate of homopolymerization of styrene in hydrocarbon solvents is known to be substantially faster that of butadiene, when a mixture of butadiene and styrene is polymerized the butadiene is consumed first [21]. Once the cross-propagation rates were determined (k and in Figure 21.1) the cause of this counterintuitive result became apparent [22]. The rate of addition of butadiene to a growing polystyryllithium chain (ksd) was found to be fairly fast, faster in fact than the rate of addition of another styrene monomer. On the other hand, the rate of addition of styrene to a growing polybutadienyllithium chain (k s) was found to be rather slow, comparable to the rate of butadiene homopolymerization. Thus, until the concentration of butadiene becomes low, whenever a chain adds styrene it is converted back to a butadienyllithium chain before it can add more styrene. Similar results were found for the copolymerization of styrene and isoprene. Monomer reactivity ratios have been measured under a variety of conditions [23]. Values for rs are typically <0.2, while values for dienes (rd) typically range from 7 to 15. Since... 

Rank the following monomers in order of their increased tendency to alternate in copolymerization with butadiene and explain your reasoning vinyl acetate, styrene, acrylonitrile, and methyl methacrylate, Hint Use Q-e values if reactivity ratios are not readily available.)... 

An examination of reported reactivity ratios (Table 6) shows that the behaviour rj > 1, r2 1 or vice versa is a common feature of anionic copolymerization. Only in copolymerizations involving the monomers 1,1-diphenylethylene and stilbene, which cannot homopolymerize, do we find <1, r2 <1 [212—215], and hence the alternating tendency so characteristic of many free radical initiated copolymerizations. Normally one monomer is much more reactive to either type of active centre in the order acrylonitrile > methylmethacrylate > styrene > butadiene > isoprene. This is the order of electron affinities of the monomers as measured polarographically in polar solvents [216, 217]. In other words, the reactivity correlates well with the overall thermodynamic stability of the product. Variations of reactivity ratio occur with different solvents and counter-ions but the gross order is predictable. 

Some commercially important examples of random free-radical copolymerizations include styrene (ri = 0.8)-butadiene (r2 = 1.4) for which rir2 = 1.1 and vinyl chloride (ri = 1.4)-vinyl acetate (r2 = 0.65) for which rir2 = 0.9. In these products the proportion of a given monomer in the copolymer depends on the feed concentrations and reactivity ratios [Eq. (7.11)]. 

The polyester resin used in this study, MR 13006 (Aristech Corporation), was supplied as a 60-wt% solution in styrene monomer. The epoxy resin, a digly-cidyl ether of bisphenol A (Epon 828), was obtained from Shell Chemical Company. The reactive liquid rubber, an amino-terminated butadiene-acrylonitrile copolymer (ATBN 1300 x 16), was provided by the BFGoodrich Company. The resin was mixed with additional styrene monomer to maintain the ratio of reactive unsaturation in the polyester-to-styrene monomer at 1 to 3. We added 1.5 wt% of tert-butylperbenzoate initiator to the solution, which we then degassed under vacuum. The mixture was poured between vertical, Teflon-coated, aluminum plates and cured under atmospheric pressure at 100 °C. In the modified compositions, the rubber was first dissolved in the styrene monomer, and then all the other components were added and the solution cured as described. In all the compositions, the ratio of the amine functions with respect to the epoxy functions was kept at 1 to ensure complete cure of the epoxy. 

The simplest diblock polymer, styrene/butadiene block polymer, is formed when the two monomers are charged into a batch reaction along with the catalysts. The reactivity ratios are such that the butadiene polymerizes first and with almost total exclusion of any styrene present. Only after all of the butadiene monomer has been consumed does the bulk of the styrene enter the polymer chain. 

There are few studies of the effect of temperature on monomer reactivity ratios [Morton, 1983]. For styrene-1,3-butadiene copolymerization by r-butyUithium in n-hexane, there is negligible change in r values with temperature with ri = 0.03, r2 — 13.3 at 0°C and ri = 0.04, = 11.8 at SO C. There is, however, a significant effect of temperature for copo-... 

An interesting consequence of the marked differences in reactivity ratios found in some of the anionic systems is that in a mixture of monomers pure blocks of one can be obtained without incorporation of the second monomer. In styrene-butadiene mixtures, the latter reacts most rapidly and can be almost completely polymerized before the styrene begins to react. As the butadiene becomes depleted, styrene is... 

Random copolymers are always found if the product rjxr2 = 1, i.e., both monomers have the same preference for monomer 1 over 2 (kn/ki2 = k2i/k22). The examples 3a and 3b are two possible random copolymers with opposite reactivity-ratios r, and tj. A typical random copolymer can be made of 1,3-butadiene, CH2=CH-CH=CH2, and styrene, CH2=CH-CgH5). 

Random Styrene-Diene Copolymers. Random copolymers of butadiene (SBR) or isoprene (SIR) with styrene can be prepared by addition of small amounts of ethers, amines, or alkali metal alkoxides with alkylhthium initiators. Random copolymers are characterized as having only small amounts of block styrene content. The amoimt of block styrene can be determined by ozonoly-sis or, more simply, by integration of the nmr region corresponding to block polystyrene segments (S = 6.5-6.94 ppm) (180). Monomers reactivity ratios of tb = 0.86 and rs = 0.91 have been reported for copolymerization of butadiene and styrene in the presence of 1 equiv of TMEDA ([TMEDAMRLi] = 1) (181). However, the random SBR produced in the presence of TMEDA will incorporate the butadiene predominantly as 1,2 imits. At 66°C, 50% 1,2-butadiene microstructure will be obtained for copolymerization in the presence of lequiv of TMEDA (134). In the presence of Lewis bases, the amounts of 1,2-polybutadiene enchainment decreases with increasing temperature. 

The expressions are an outcome of the terminal model theory with several steady-state assumptions related to free-radical fiux (14,23). Based on copolymerization studies and reactivity ratios, chloroprene monomer is much more reactive than most vinyl and diene monomers (Table 1). 2,3-Dichloro-l,3-butadiene is the only commercially important monomer that is competitive with chloroprene in the free-radical copolymerization rate. 2,3-Dichlorobutadiene or ACR is used commercially to give crystallization resistance to the finished raw polymer or polymer vulcanizates. a-Cyanoprene (1-cyano-l,3-butadiene) and /3-cyanoprene (2-cyano-1,3-butadiene) are also effective in copolymerization with chloroprene but are difficult to manage safely on a commercial scale. Acrylonitrile and methacrylic acid comonomers have been used in limited commercial quantities. Chloroprene-isoprene and chloroprene-styrene copolymers were marketed in low volumes during the 1950s and 1960s. Methyl methacrylate has been utilized in graft polymerization particularly for vinyl adhesive applications. A myriad of other comonomers have been studied in chloroprene copolymerizations but those copolymers have not been used with much commercial success. 

Because of the complicating effects of counterion and solvent associated with anionic polymerization, relatively few reactivity ratios have been determined for anionic systems. Typical reactivity ratios for the anionic copolymerization of styrene and a few other monomers are shown in Table 8.3. Most of the values were determined from the copolymer composition equation [Eq. (7.11) or (7.18)]. A dramatic effect of solvent is seen with styrene-butadiene copolymerization, where a change from the nonpolar hexane to the highly solvating THF reverses the order of reactivity. Again in the case of hydrocarbon solvent, the reaction temperature shows a minimal in uence on reactivity ratios, while in the case of polar solvents, such as THF, the reactivity ratios vary considerably, which has been rationalized by considering the solvation of carbon-lithium bond. Thus as the temperature is increased (from -78°C to 25°C), the extent of solvation by THF is expected to decrease, resulting in more covalent carbon-lithium bond. 

Calculated values based on monomer feed compositions, conversions and reactivity ratios of 1.55 and 0.48 for butadiene and styrene, respectively. 

Studies of the copolymerizations of 1,1-diphenylethylene and dienes showed rather different behavior compared with the copolymerizations of styrene and 1,1-diphenylethylene [125, 133-136]. The monomer reactivity ratios for copolymerizations of dienes with DPE are shown in Table 7. When butadiene was copolymerized with 1,1-diphenylethylene in benzene at 40 °C with -butyl-lithium as initiator, the monomer reactivity ratio for butadiene, ri, was 54 this means that the addition of butadiene to the butadienyl anion is 54 times faster than addition of 1,1-diphenylethylene to the butadienyl anion [133]. This unreactivity of poly(butadienyl)lithium towards addition to DPE was also observed in studies of end-capping of poly(butadienyl)lithium with DPE in hydrocarbon solution (see Sect.3.3) [109, 111]. Because of this unfavorable monomer reactivity ratio, few DPE units would be incorporated into the co-... 

First, there is a diene-rich block a middle block follows which is initially richer in butadiene with a gradual change in composition until eventually it becomes richer in styrene a final block of styrene completes the stmcture. Thus, there is compositional homogeneity between polymer chains, but there is compositional heterogeneity within each polymer chain because of the living nature of these polymerizations and the disparity in the monomer reactivity ratios. 

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