Acidic polystyrene based resins are not very suitable for use in reactive distillation column as well as for temperatures greater than 393 K. To overcome these problems porous silica has been coated with divinylbenzene (DVB) or styrene-DVB and polymerized using azoisobutyronitrile as initiator. Sulfonation of the polymer was carried out by using chlorosulfonic acid. Thus acidic polymeric material of exchange capacity of up to 0.41 meq/g has been obtained, in convenient size of 2-5 mm which can be directly used in reactive distillation column as demonstrated for methylal preparation in this paper and which is also suitable for use up to 433 K, verified by successfully carrying out reaction of phthalic anhydride with 2-ethyl-hexanol. Reusability of this catalyst was also tested by performing the reaction of iso-propyl alcohol with acetic acid.