Establishing high-speed and reliable underwater acoustic networks among multiunmanned underwater vehicles (UUVs) is basic to realize cooperative and intelligent control among different UUVs. Nevertheless, different from terrestrial network, the propagation speed of the underwater acoustic network is 1500 m/s, which makes the design of the underwater acoustic network MAC protocols a big challenge. In accordance with multichannel MAC protocols, data packets and control packets are transferred through different channels, which lowers the adverse effect of acoustic network and gradually becomes the popular issues of underwater acoustic networks MAC protocol research. In this paper, we proposed a control packet collision avoidance algorithm utilizing time-frequency masking to deal with the control packets collision in the control channel. This algorithm is based on the scarcity of the noncoherent underwater acoustic communication signals, which regards collision avoiding as separation of the mixtures of communication signals from different nodes. We first measure the W-Disjoint Orthogonality of the MFSK signals and the simulation result demonstrates that there exists time-frequency mask which can separate the source signals from the mixture of the communication signals. Then we present a pairwise hydrophones separation system based on deep networks and the location information of the nodes. Consequently, the time-frequency mask can be estimated.