On the first page of MilnorKervaire's paper "Bernoulli numbers, homotopy groups, and a theorem of Rohlin", they assert without proof or reference that if $M$ is a compact connected oriented differentiable $4$manifold such that $w_2(M)=0$, then $M$ is almost parallelizable, that is, for all $x_0 \in M$ the tangent bundle of $M \setminus x_0$ is trivial. Try as I might, I cannot figure out how to prove this. Can someone help me?

You want to trivialise the restriction of the tangent bundle to the 3skeleton of $M$. Since $\pi_0 O(4) = \pi_1 O(4) = Z/2$, there are obstructions $w_1(E) \in H^1(X; Z/2)$ and $w_2(E) \in H^2(X;Z/2)$ to trivialising a rank 4 bundle over the 1 and 2skeleta of a cell complex $X$. Because $\pi_2 O(4)$ is trivial, there is no further obstruction to extending a trivialisation from the 2skeleton to the 3skeleton. This is outlined in a nice way at the beginning of chaper 3 in Hatcher's book on vector bundles. 

