A new material can be created with bpy.data.materials.new(). You assign a material to a face by setting it's material_index, which is the material's index from it's location in object.material_slots, we need to use the length of material_slots to know the index of the material we just added to the list.

import bpy

obj = bpy.context.object
obj.data.materials.clear(update_data=True)

for f in obj.data.polygons:
    m = bpy.data.materials.new('FaceMat' + str(f.index))
    m.diffuse_color = Color((0.01*f.index,0.02*f.index,0.03*f.index))
    obj.data.materials.append(m)
    f.material_index = len(obj.data.materials)-1

This is a simple example that sets the diffuse colour used by BI which is also used by cycles for the viewport colour. To create a cycles material you will want to create nodes as well.

You could also do it in two parts, one loop to create materials and another to assign a material based on the material name. This way you could create 10 materials and distribute them across the object.

obj.data.materials.append(bpy.data.materials[mat_name])

A new material can be created with bpy.data.materials.new(). You assign a material to a face by setting it's material_index, which is the material's index from it's location in object.material_slots, we need to use the length of material_slots to know the index of the material we just added to the list.

import bpy

obj = bpy.context.object
obj.data.materials.clear()

for f in obj.data.polygons:
    m = bpy.data.materials.new('FaceMat' + str(f.index))
    # for 2.79 remove the ,1.0 at the end
    m.diffuse_color = (0.01*f.index,0.02*f.index,0.03*f.index, 1.0)
    obj.data.materials.append(m)
    f.material_index = len(obj.data.materials)-1

This is a simple example that sets the diffuse colour used by BI which is also used by cycles for the viewport colour. To create a cycles material you will want to create nodes as well.

You could also do it in two parts, one loop to create materials and another to assign a material based on the material name. This way you could create 10 materials and distribute them across the object.

obj.data.materials.append(bpy.data.materials[mat_name])