Merging the Maritime provinces (and adding Newfoundland and Labrador if desired) would make a certain amount of sense form a efficiency standpoint, collapsing four sets of bureaucracies, legislatures, crown corporations ext into one. Of course, if the example of the GTA is any indication, the largest, most expensive and inefficient bureaucracies and public service unions would survive....
Despite the meanderings of "post national" theorists, I don't see that micro nations or distributed republics have any great advantages over conventional States, the modern nation state has been around since 1648 indicating it has a very solid foundation and has been able to displace all potential alternative models for centuries. Small nations formed out of the wreakage of larger failed states may or may not succeed, but I believe that is more a matter of the sort of culture the people living in that state practice and share.
If the Canadian west were to hypothetically separate, they would probably do well; they have an entrepreneurial culture and are busy taking the idea of small "c" conservatism to heart (look at the Saskatchewan Party's turnaround of that province, and the emergence of the Wild Rose Alliance in Alberta). Quebec, blessed with a treasure trove of natural resources, would likely fail if they separated, since they have a very Statist culture. Sadly, the Maritimes has also fallen for the Statist meme, and may end up living off oil and gas in much the same way the Gulf States do (although we might not see extravagant construction booms such as in Dubai).
Regardless of their internal cultures, I suspect that if Confederation were to split along these lines, the United States would simply not choose to deal with the remnants of former Quebec or the Maritimes except as providers of raw materials (to avoid having to assume the debts and obligations of these polities), while being much more receptive of an economically dynamic West as either a client or allied nation.
Now you could have roving bands of fur trappers trying to sneak past the customs posts and border fences between Quebec and the United States, or maybe the Irvings deciding to take the term "oil baron" literally in a fractured post confederation Canada, but that is about as realistic as the Space Patrol delivering ice from Saturn to Earth or the United States invading Canada....