Copolymers of vinylidene chloride (VDC) and acrylates or methacrylates were investigated by calorimetric (DSC) and infrared spectroscopic methods to determine glass transition temperature and crystallization behavior. The final crystallinity of some annealed copolymers of VDC and methyl acrylate (MA) or methyl methacrylate (MMA) was studied by means of WAXS measurements. It was found that: (i) the glass transition temperature of copolymers of VDC and acrylates goes through a maximum as a function of the composition. The maximum shifts toward higher concentrations of VDC in the copolymer with increasing length of the ester group. (ii) However, for copolymers of VDC and methacrylates one observes a monotonic rise in the glass transition temperature with increasing concentration of the methacrylate, that can be described by the equation of Gordon and Taylor. (iii) For a given comonomer, the crystallization rate increases with increasing VDC content and, moreover, for a given VDC content it is slowest with methyl acrylate and fastest with ethylhexyl acrylate. Therefore, for a given crystallization rate, the copolymers of VDC and methyl acrylate contain the highest weight fraction of VDC. However, on a molar basis the differences are rather small. Analogous behavior is observed for the copolymers of VDC and acrylates or methacrylates. (iv) The final crystallinity of the annealed copolymers decreases linearly with decreasing VDC content. From this linear decrease, the limiting VDC concentration for zero crystallinity was extrapolated to about 75 mol‐% VDC. These values are slightly lower than those estimated from infrared spectroscopy. Consequently, the final crystallinity of the copolymers studied is influenced by the VDC content rather than by the comonomer type. (v) The final crystallinity of the VDC homopolymer is determined as 57 ± 2 wt.‐% in agreement with literature data. The crystallinity of the copolymers of VDC with different acrylates or methacrylates can then be estimated as a function of the composition.

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Die angefuhrten Ergebnisse konnen a) verallgemeinert werden fur zahlreiche ringoffnende Polymerisationen, bei denen kristallines Polymeres entsteht, und haben b) Bedeutung fur die Theorie der Copolymerisation in solchen Systemen.