Solubilities of N-[(4-bromo-3,5-difluorine) phenyl]-acrylamide in methanol–ethanol solution

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Abstract

N-[(4-bromo-3,5-difluorine)phenyl]acrylamide is a new monomer for polymerization reactions. Information on its corresponding solid–liquid equilibrium is essential for industrial product and process design. Using a laser detecting system, solubility data were measured for N-[(4-bromo-3,5-difluorine)phenyl]acrylamide dissolved in different compositions of methanol–ethanol mixtures at the temperature range from 287.75 K to 339.55 K. The solubility data were correlated with Apelblat equation and Buchowski–Ksiazczak λh equation. The Buchowski–Ksiazczak λh equation was found to regress the solubility data much better than the Apelblat equation.

Introduction

Fluorine-containing polymers are particularly attractive and useful compounds because of their unique properties including high thermal, chemical, aging and weather resistance, low dielectric constants, refractive index, surface energy and flammability [1], [2], [3]. There are various approaches for preparing fluorine-containing acrylate emulsion, such as synthesizing core-shell fluorine-containing polyacrylate emulsion with fluorine-free acrylate and fluorine-containing acrylate monomers [4], [5], [6], [7], [8], [9].

N-[(4-bromo-3,5-difluorine)phenyl]acrylamide (BDPA, Fig. 1) is a new fluorine-containing acrylate monomer for polymerization reactions. BDPA was synthesized by the interaction of 4-bromo-3,5-difluoroaniline with acryloyl chloride in presence of triethylamine. Crude BDPA was gained after concentrating and filtrating. For extensive fluorine-containing polymers investigation, crude BDPA has to be purified by crystallization. In order to improve the purity and yield of BDPA, the solubility data of BDPA in different solvents are required.

In this paper, the solubilities of BDPA in different compositions of methanol–ethanol mixtures were experimentally determined using the synthetic method by a laser monitoring observation technique [10]. The experimental data were correlated using the modified Apelblat equation and Buchowski–Ksiazczak λh equation.

Section snippets

Materials

BDPA was synthesized by ourselves as the following method: 200 ml ethyl acetate, 32.1 g 4-bromo-3,5-difluoroaniline, 25 g sodium bicarbonate and 0.5 g ethyl hydroxylamine were put into a 500 ml 4-mouth flask, respectively, then 22 ml acryloyl chloride was dropwise added, the mixture was maintained for 10 h at the temperature of 293.15 K, followed by 15 h reflux. Ethyl acetate was removed by distillation, and then cooled to room temperature, BDPA [12 g, mp 454.85–455.45 K, 1H NMR (CDCl3, 400 MHz) δ:

Results and discussion

The solubilities of BDPA in different compositions of methanol–ethanol mixtures were determined and listed in Table 1 and Fig. 2. Mole fraction, xi values in Table 1, Table 2, Table 3 are the average values taken from three test tubes for the same solution. xe is the mole fraction of methanol in methanol–ethanol mixtures.

To describe solid–liquid equilibrium, the relationship between solubility and temperature can be described as [11]ln1γxx=ΔfusHRTtTtT1ΔCpRTtT1+ΔCpRlnTtTwhere γx is the

Conclusions

Using the laser monitoring observation technique, the solubility of BDPA in methanol–ethanol solution as a function of temperature was determined in this study. Depending on Table 1, Table 2, Table 3 and Fig. 2, some conclusions can be obtained: (1) the solubilities of BDPA in all selected solutions slightly increase with increasing temperature; (2) the solubilities of BDPA in methanol–ethanol mixtures decrease with increasing the mole fraction of methanol in the methanol–ethanol solutions; (3)

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