$\angle (2\vec{a},-2\vec{b})=\angle (\vec{a},-\vec{b})=180-\angle(\vec{a},\vec{b})$
The explanation why each equality holds:
For the first equality:
$$
\cos{\angle (2\vec{a},-2\vec{b})}=\frac{4\vec{a}\vec{b}}{2||\vec{a}||2||\vec{b}||}= \cos{\angle (\vec{a},-\vec{b})}
$$
For the second equality:
$$
\cos{\angle (\vec{a},-\vec{b})}=-\frac{\vec{a} \vec{b}}{||\vec{a}||||\vec{b}||}=-\cos{\angle (\vec{a},\vec{b})}\Rightarrow \angle (\vec{a},-\vec{b})=180-\angle (\vec{a},\vec{b})=120
$$
Note that when we refer to the angle of two vectors we consider the angle that is between $0$ and $180$ so when we found $\cos{\theta}=-\cos{60}=-\frac 1 2$ we have that $\theta=120$.