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The proton fraction in β-stable neutron stars is investigated within the framework of the Skyrme-Hartree-Fock theory using the extended Skyrme effective interaction for the first time. The calculated results show that the proton fraction disappears at high density, which implies that the pure neutron matter may exist in the interior of neutron stars. The incompressibility of the nuclear equation-of-state is shown to be more important to determine the proton fraction. Meanwhile, it is indicated that the addition of muons in neutron stars will change the proton fraction. It is also found that the higher-order terms of the nuclear symmetry energy have obvious effects on the proton fraction and the parabolic law of the nuclear symmetry energy is not enough to determine the proton fraction.