As the European Union urged dialogue to ease the standoff between separatists in the northeastern region and Madrid, Catalan leaders said they could unilaterally declare independence as early as Monday.
The tone of the crisis sharpened with Catalonia's president denouncing the king's intervention and Spain's government rejecting any possible talks.
"The government will not negotiate over anything illegal and will not accept blackmail," said a statement from Prime Minister Mariano Rajoy's office.
The dispute is Spain's worst political crisis in decades and images of police beating unarmed Catalans taking part in Sunday's banned independence vote sparked global concern.
Spain's key IBEX 35 stock index plunged by more than three per cent today in the ongoing turbulence, with some big Catalan banks down more than five percent.
"Political risk is back on the agenda in Europe," NFS Macro analyst Nick Stamenkovic told AFP.
After meetings in the regional parliament today, pro- independence lawmakers called a full session next Monday to debate the final results of the vote.
Mireia Boya of the radical leftwing separatist CUP said it would be "a plenary to proclaim the republic" of independent Catalonia.
King Felipe VI on Tuesday branded the independence drive illegal and undemocratic, throwing his weight behind the national government.
Catalan leaders "with their irresponsible conduct could put at risk the economic and social stability of Catalonia and all of Spain", he said.
Accusing them of "disloyalty", the king said that the state had to "ensure constitutional order".
Puigdemont angrily rejected this, saying in a televised address: "The king has adopted the (national) government's position and policies which have been disastrous with regard to Catalonia. He is deliberately ignoring millions of Catalans."
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