Chlorine containing polyether sulfone polymers and preparation t

Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From phenol – phenol ether – or inorganic phenolate

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528219, C08G 8106

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045337217

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DESCRIPTION

The present invention relates to a novel chlorine-containing polyether-sulfone polymer excellent in the flame retardancy, heat resistance, transparency, and water resistance, which is obtained by polymerizing at least one aromatic tri- or tetra-halide compound with at least one dihydric phenol dialkali metal salt, and also to a process for the preparation of this polymer.
A process for preparing a linear polyarylene-polyether-sulfone polymer by reacting a dihydric phenol dialkali metal salt with an activated dihalobenzenoid compound has been known (see Japanese Examined Patent Publication No. 42-7799). Furthermore, there has been proposed an improved process for the preparation of the above-mentioned polymer (see Japanese Examined Patent Publication No. 45-21318, No. 46-18146, and No. 46-21458).
Linear polyarylene-polyether polymers obtained according to these processes are excellent in various properties such as the heat resistance at high temperatures, the mechanical characteristics, and the alkali resistance, and they are widely used in various fields.
However, the flame retardancy of these polymers is not completely satisfactory as pointed out hereinafter. For example, when a film having a thickness of 0.1 mm is ignited, burning is continued even after the fire source has been removed.
It also is known that a polyarylene-ether-sulfone polymer containing a halogen atom on the aromatic nucleus can be obtained by reacting 4,4'-dichlorodiphenylsulfone with a dialkali metal salt of a nucleushalogenated bisphenol, as disclosed in the above-mentioned Japanese Examined Patent Publication No. 42-7799. However, in this process, since the bisphenol having a halogen atom at the ortho-position to the hydroxyl group of the bisphenol is used, the nucleophilic reactivity of the phenoxide is drastically reduced by the influence of the electron-attractive property of the halogen atom and the steric hindrance by the substitution at the ortho-position. Therefore, the process is disadvantageous in that a high temperature or a long time is necessary for completion of the reaction. Moreover, the obtained polymer is readily colored and is not advantageous as a polymeric material.
In "Polymer", volume 18, page 360 (1977), T. I. Atwood teaches that a chlorinated polyether-sulfone polymer can be obtained by melt-polymerizing a compound represented by the following structural formula: ##STR2## at such a high temperature as 310.degree. C. In a polymer obtained by the polymerization conducted at such a high temperature as described above, undesirable coloration or gelation is often caused. Moreover, since the melt polymerization technique is adopted, control of the viscosity is restricted. Namely, if it is intended to obtain a polymer having a high molecular weight, the viscosity of the reaction mixture should inevitably be increased, with the result that mechanical stirring becomes difficult and the temperature in the reaction mixture becomes uneven.
Furthermore, there is proposed a process in which 3,3',4,4'-tetrachlorodiphenylsulfone is polymerized with 4,4'-dihydroxydiphenylsulfone in the presence of anhydrous potassium fluoride at a temperature of 240.degree. C. for 23 hours (see Japanese Unexamined Patent Publication No. 49-4800).
According to this process, a chlorinated polysulfone having a low reducing viscosity of about 0.34 may be obtained without formation of a gelation product. However, this process is not industrially advantageous, because a high reaction temperature and a long time are necessary, and is not advantageous from the economic viewpoint, because a fluoride which is more expensive than a hydroxide or carbonate should be used at least in a stoichiometric amount. Moreover, since fluoride is used, a reaction vessel composed of glass or metal cannot be used. Therefore, this process is still insufficient in various points.
Under this background, we made researches with a view to obtaining polymers while eliminating the foregoing defects. As the result, we found that when (A) at least one aromatic tri

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