Some properties of copolymers of vinylidene chloride with acrylates and methacrylates, Part 1

Abstract

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.

Acrylate–vinylidene chloride copolymers derived from corresponding water‐borne latexes: Influence of acrylate units on their potential as heavy‐duty anticorrosive coating materials

“…70% VDC content. The variations in T g are similar to those reported by Penzel, Kodani, and Powell . When the VDC contents in the copolymers are the same, the T g values of the copolymers are in the ordering of MA–VDC > EA–VDC > BA–VDC > HA–VDC ≥ EHA–VDC.…”

“…FTIR is a sensitive method for detecting crystallization in acrylate–VDC copolymers . In the FTIR of pure PVDC, two absorption bands at ca.…”

“…Aqueous latexes of poly(vinylidene chloride) (PVDC) or its copolymers can be synthesized by emulsion polymerization, and they are much cheaper than other water‐borne coating materials applicable in heavy‐duty anticorrosion, such as epoxide resins. PVDC films have excellent barrier properties, better than those of nylon, ethylene vinyl alcohol, poly(ethylene terephthalate), and low‐density polyethylene . However, its adhesion to metal is very poor.…”

Dual-Emissive Coating Films Prepared from Water-Borne Latexes of Acrylate–Vinylidene Chloride Copolymers: Their Room-Temperature Phosphorescence Properties and Sensing Abilities toward Solvents

“…It is clear that all the acrylate–VDC copolymer films with a VDC content of ≥85% are semicrystalline, a characteristic of the typical PVDC crystallization peaks at ca. 15.5°, 24.6°, and 32.1°. , As for BA–VDC copolymer films, BA–VDC81 with a VDC content of <85% is also semicrystalline. However, the typical PVDC crystallization peaks are weak and broad in all these semicrystalline polymers, which implies that all these semicrystalline polymers have a low crystallization degree.…”

“…Why do the soft acrylate–VDC copolymer films with the high VDC content show strong RTP emission? It is known that PVDC chains can densely pack together, which make PVDC become one of the best barrier polymers against water and oxygen gases, , better than those most commonly used barrier polymers of nylon, poly­(vinyl alcohol), poly­(ethylene terephthalate), and low-density polyethylene . The densely packing nature of PVDC segments also leads to their poor compatibility with other materials, which can be supported by the fact that all the as-prepared acrylate–VDC copolymers, especially those with the higher VDC content, have very poor solubility in all the organic solvents.…”