  In this paper, we study a class of matrix-valued orthogonal polynomials
(MVOPs) that are related to 2-periodic lozenge tilings of a hexagon. The
general model depends on many parameters. In the cases of constant and
$2$-periodic parameter values we show that the MVOP can be expressed in terms
of scalar polynomials with non-Hermitian orthogonality on a closed contour in
the complex plane. The 2-periodic hexagon tiling model with a constant
parameter has a phase transition in the large size limit. This is reflected in
the asymptotic behavior of the MVOP as the degree tends to infinity. The
connection with the scalar orthogonal polynomials allows us to find the
limiting behavior of the zeros of the determinant of the MVOP. The zeros tend
to a curve $\widetilde{\Sigma}_0$ in the complex plane that has a
self-intersection. The zeros of the individual entries of the MVOP show a
different behavior and we find the limiting zero distribution of the upper
right entry under a geometric condition on the curve $\widetilde{\Sigma}_0$
that we were unable to prove, but that is convincingly supported by numerical
evidence.
