Hyperbranched Polymers Formed Through Self‐Condensing Vinyl Polymerization in a Continuous Stirred‐Tank Reactor (CSTR): 2. Branched Architecture

Abstract

The Monte Carlo simulation method proposed in Part 1 of this series is used to investigate the branched architecture of hyperbranched polymers formed through self‐condensing vinyl polymerization (SCVP) in a continuous stirred‐tank reactor (CSTR). The degree of branching (DB) at large chain length (P) limit, DBinf, does not change with the mean residence time truet¯. The value of DBinf is larger than the corresponding batch polymerization. The relationship between the mean‐square radius of gyration <s2>0 and P does not change with truet¯, and high molecular weight (MW) polymers obtained in a CSTR are much more compact than those formed in batch polymerization. At least for the high MW polymers, CSTR is advantageous to synthesize compact hyperbranched polymers.

Detailed Structural Analysis of the Hyperbranched Polymers Formed in Self‐Condensing Vinyl Polymerization

“…On the other hand, it was reported earlier that the relationship between Rg 2 and P is kept approximately constant even when the ξ–value is changed for a given reactivity ratio, r . The variation of Rg 2 data is large for large polymers, and both Rg 2 and P were converted to the logarithmic scale to suppress the variation in the earlier investigation . On closer look at Figure 7 of ref.…”

“…On closer look at Figure 7 of ref. , however, one would notice that the curve of Rg 2 for a smaller ξ bends down slightly for large polymers, even though the difference is rather small for the most chain length region. In the present investigation, the normal scale is applied to estimate the expected Rg 2 .…”

“…On the other hand, DB inf ‐value is larger for a CSTR than for a batch reactor, as one can find by comparing Figure and Figure . Larger DB inf for a CSTR applies, irrespective of the magnitude of r …”

“…Larger ξ‐value leads to a higher level of conversion. Figure shows the expected DB‐value for the given P ‐value for the system with r = 1, when the ξ‐value is changed from 0.3 to 0.7 . Again, the value of DB inf is constant with zero variance, irrespective of the ξ‐value.…”

“…Expected DB of the polymer molecules with P , for an SCVP with r = 1 conducted in a CSTR, when the ξ‐value is changed from 0.3 to 0.7. Reproduced with permission …”