asp.net doesn't know about any changes you make to server controls via javascript so it can't see your new items. If you are manipulating the dropdown via ajax then don't use an asp:DropDownList, instead just use a normal html <select> like
<select name="ddlCountry" id="ddlCountry">
<option value="UK">United Kingdom</option>
</select>
then in your click event you read the value using
string country = Request.Form["ddlCountry"];